434 Lewkowski and Dzie¸gielewski
5.6 mL) was added dropwise for 15 min. The mix-
ture was stirred for 1 h at room temperature. Then,
a solution of an appropriate Schiff base (5 mmol)
in dry dichloromethane was added, and the mix-
ture was refluxed for 4 h. Then, the solution was
evaporated in vacuo, and the residue was dissolved
in dry methanol. It was stirred for 30–45 min until
precipitation of a solid, which was filtered off and
collected. In the case, if the solid did not precipi-
tated, 10–20 mL of propylene oxide was added and
the mixture was refrigerated for 3–7 days. Then
the solid was filtered off and collected. Products
were purified by dissolution in 10% aqueous NaOH
followed by precipitation by acidification with 1 M
HCl.
53.44; H, 5.71; N, 5.67;. Found: C, 53.83; H, 5.85; N,
5.48.
1,4-Phenylene-bis-(N-(p-methoxyphenyl)amino-
methylphosphonic Acid) 3e. Yield = 95% (2.40 g);
mp: 186–188◦C. 1H NMR (NaOD/D2O, 200 MHz):
δ 7.18 (s, C6H4, 4H); 6.56 (d, J = 9.1 Hz, Part of
AAꢀXXꢀ system, 4H); 6.48 (d, J = 9.1 Hz, Part of
2
AAꢀXXꢀ system, 4H); 4.22 (d, JPH = 20.3 Hz, PCH,
2H); 3.48 (s, OCH3, 6H). 31P NMR (NaOD/D2O,
81 MHz): δ 14.76. Elemental analysis: Calcd for
.
C22H26N2O8P2·2H2O: C, 48.54; H, 5.55; N, 5.14.
Found: C, 48.95; H, 5.45; N, 5.04.
1,4-Phenylene-bis-(N-(m-methylphenyl)aminome-
thylphosphonic Acid) 3f. Y = 32% (0.77 g); mp:
1
160–162◦C. H NMR (DMSO-D6, 200 MHz): δ 7.35
1,4-Phenylene-bis-(N-benzylaminomethylphosph-
onic Acid) 3a. Yield = 92% (2.2 g); mp 242–244◦C.
1H NMR (NaOD/D2O, 200 MHz): δ 7.27 (s, C6H4,
(s, C6H4, 4H); 6.84 (dd, J = 7.9 and 7.2 Hz, m-C6H4,
2H); 6.48 (s, m-C6H4, 2H); 6.41 (d, J = 7.9 Hz,
m-C6H4, 2H); 6.29 (d, J = 7.2 Hz, m-C6H4, 2H); 4.57
2
4H); 7.21 (m, PhH, 10 H); 3.61 (d, JPH = 16.5 Hz,
2
(d, JPH = 23.2 Hz, PCH, 2H); 2.09 (s, CH3, 6H). 31P
2H); 3.57 (d, J = 12.4 Hz, CHAHB, 2H); 3.43 (d,
J = 12.4 Hz, CHAHB, 2H). 31P NMR (NaOD/D2O,
NMR (DMSO-D6, 81 MHz): δ 17.20; 17.10 (10:1).
.
3
Elemental analysis: Calcd for C22H26N2O6P2 · /2H2O:
81 MHz): δ 15.13. Elemental analysis: Calcd for
.
C, 52.49; H, 5.81; N, 5.56. Found: C, 52.65; H, 6.10;
N, 5.22.
C22H26N2O6P2·2H2O: C, 51.57; H, 5.90; N, 5.47.
Found: C, 51.89; H, 5.12; N, 5.51.
1,4-Phenylene-bis-(N-(m-methoxyphenyl)amino-
methylphosphonic Acid) 3g. Yield = 46% (1.17 g);
mp: 236–238◦C. 1H NMR (NaOD/D2O, 200 MHz):
δ 7.18 (s, C6H4, 4H); 6.84 (dd, J = 8.0 and 8.2 Hz,
m-C6H4, 2H); 6.15 (m, m-C6H4, 2×2H); 6.05 (m,
m-C6H4, 2H); 4.25 (d, 2 JPH = 20.2 Hz, PCH, 2H); 3.42
1,4-Phenylene-bis-(N-furfurylaminomethylphos-
phonic Acid) 3b. Yield = 79% (1.80 g); mp: 190–
1
193◦C. H NMR (NaOD/D2O, 200 MHz): δ 7.25 (m,
CH5fur, 2H); 7.14 (s, C6H4, 4H); 6.17 (dd, J = 1.8 and
3.2 Hz, H4fur, 2H); 6.00 (d, J = 3.2, Hf3ur, 2H); 3.49
(d, J = 13.9 Hz, CHAHB, 2H); 3.42 (d, J = 13.9 Hz,
(s, OCH3, 6H). 31P NMR (NaOD/D O, 81 MHz): δ
.
2
2
CHAHB, 2H); 3.61 (d, JPH = 24.1 Hz, 2H). 31P NMR
14.45; 14.39 (3:2). EI-MS: m/z = 508 [M+]; 346 [M+
(NaOD/D O, 81 MHz): δ 15.09. Elemental analysis:
.
2
− (PO3H2)2].
1
Calcd for C18H22N2O8P2 /2H2O: C, 46.46; H, 4.98; N,
6.02. Found: C, 46.19; H, 5.01; N, 5.91.
1,4-Phenylene-bis-(N-(p-Methoxyphenyl)amino-
methylphosphonic Acid) di-(R)-α-Methyl-benzyl-
ammonium Salt (4e)
1,4-Phenylene-bis-(N-t-butylaminomethylphos-
phonic Acid) 3c. Yield = 80% (1.63 g); mp: 214–
216◦C. 1H NMR (NaOD/D2O, 200 MHz): δ 7.27
1,4-Phenylene-bis-(N-(p-methoxyphenyl)aminome-
thylphosphonic acid) (3e) (0.95 g, 5 mmol) was
dissolved in acetone, and (R)-α-methylbenzylamine
(2.42 g, 20 mmol) was added during vigorous stir-
ring. The mixture was stirred at room temperature
for 24 h; the precipitated solid was filtered off, dried,
and carried out NMR study. Before crystallization
[α]20 = +10.89◦ (c = 0.016) after [αχ]20 = +6.07◦
(c= 0.016).
2
(s, C6H4, 4H); 3.62 (d, JPH = 19.7, PCH, 2H);
0.64 (s, C(CH3)3, 18H). 31P NMR (NaOD/D2O,
81 MHz): δ 16.64. Elemental analysis: Calcd for
.
C16H30N2O6P2·3H2O: C, 41.56; H, 7.85; N, 6.06.
Found: C, 41.92; H, 7.94; N, 5.52.
1,4-Phenylene-bis-(N-(p-methylphenyl)aminome-
thylphosphonic Acid) 3d. Yield = 93% (2.23 g); mp:
183–185◦C. H NMR (NaOD/D2O, 200 MHz): δ 7.11
1H NMR (DMSO-D6, 200 MHz): δ 7.44 (m, ArH,
4H); 7.31 (m, ArH, 6H); 7.12 (s, C6H4, 4H); 6.56 (d,
J = 8.9 Hz, part of AAꢀXXꢀ system, 4H); 6.48 (d,
J = 8.9 Hz, part of AAꢀXXꢀ system, 4H); 4.15 and
1
(s, C6H4, 4H); 6.72 (d, J = 7.7 Hz, Part of AAꢀXXꢀ
system, 4H); 6.37 (d, J = 7.7 Hz, Part of AAꢀXXꢀ sys-
tem, 4H); 4.19 (d, 2 JPH = 20.4 Hz, PCH, 2H); 1.93 (s,
2
CH3, 6H). 31P NMR (NaOD/D O, 81 MHz): δ 14.76.
4.11 (2d, JPH = 21.6 Hz, PCH, 2H); 4.04 (q, J =
.
2
Elemental analysis: Calcd for C22H26N2O6P2·H2O: C,
5.1 Hz, CHCH3, 2H); 3.58 (s, OCH3, 6H); 1.39 (d,
Heteroatom Chemistry DOI 10.1002/hc