622 Michalska, Boduszek, and Olszewski
−1
129.1, 129.0, 128.7, 128.6, 128.2, 127.3, 127.2, 124.4,
122.2, 120.9, 120.8, 65.36 (OCH2), 51.24 (CHP) (d,
JCP = 13.72 Hz), 43.0, 15.45 (CH3). 31P NMR (D2O):
=
(neat): 3296 (NH), 1191 (P O), 1069 (P-O) cm .
HRMS Calcd for C29H26N2OP (M + H)+ 449.1704.
Found 449.1896.
=
δ = 19.84 (s). IR (neat): 3422 (NH), 1169 (P O),
1044 (P-O) cm−1. HRMS Calcd for C21H26N2O3P
Synthesis of Quinolin-2, -3 and -4-yl-(amino)
methylphosphonic Acids 6a-f
(M + H)+ 385.1603. Found 385.1705.
To a solution of crude imine 2 (prepared as described
above, 2.5 mmol) in CH2Cl2 (25 mL), trimethyl phos-
phite (0.32 g, 2.5 mmol) was added, followed by
bromotrimethylsilane (1.6 g, 10 mmol). The mixture
was stirred for 24 h at room temperature and evap-
orated under reduced pressure. The resulted oil was
treated with methanol (5 mL) and refrigerated for
several hours. The products, quinolin-2, -3, and -4-yl-
(amino)methylphosphonic acids 6a–f, separated as
white solids and were collected by filtration, washed
with diethyl ether (15 mL), and dried in air.
Preparation of Quinolin-4 and -2-yl-(amino)
methyldiphenylphosphine Oxides 4a–d
Protocol described above for the preparation of es-
ters 3a–d was followed. Here, diethyl phosphite
was replaced by diphenylphosphine oxide. Crude
diphenylphosphine oxides 4 were purified by crystal-
lization from a mixture of toluene and hexane (1:1).
Quinolin-4-yl-methyl(N-butylamino)diphenylphos-
phine Oxide (4a): White solid; yield 77%; mp
140–144◦C. 1H NMR (CDCl3): δ = 8.83 (d, 1H,
Qu-2 J = 4.55 Hz), 7.89–7.26 (m, 15H, Qu-6, Qu-7,
Qu-8, Qu-3, Qu-9 and Phs), 5.38 (d, 1H, CH-P
J = 11.67 Hz), 2.52–2.45 (m, 2H, CH2), 1.35–1.15
(m, 2H, CH2), 0.85–0.76 (m, 2H, CH2), 0.59–0.54 (m,
3H, CH3).31P NMR (CDCl3): δ = 31.18 (s).
Quinolin-2-yl-methyl(N-butylamino)phosphonic
Acid (6a): White solid; yield 57%; mp 194–196◦C.
1H NMR (D2O): δ = 8.90 (d, 1H, Qu-4 J = 8.46 Hz),
8.09–7.22 (m, 5H, Qu-6, Qu-7, Qu-8, Qu-3, Qu-9),
4.12 (d, 1H, CH-P J = 16.69 Hz), 2.70–2.56 (m,
2H, CH2), 1.35–1.29 (m, 2H, CH2), 0.96–0.89 (m,
2H, CH2), 0.49–0.44 (m, 3H, CH3).31P NMR (D2O):
δ = 3.90 (s).
Quinolin-4-yl-methyl(N-benzylamino)diphenyl-
phosphine Oxide (4b): White solid; yield 65%; mp
150–156◦C. 1H NMR (CDCl3): δ = 8.87 (d, 1H,
Qu-2 J = 4.79 Hz), 7.82–7.05 (m, 20H, Qu-6, Qu-7,
Qu-8, Qu-3, Qu-9 and Phs), 5.25 (d, 1H, CH-P
J = 12.20 Hz), 3.60 (dd, 2H, CH2Ph J = 13.23 Hz).
13C NMR (CDCl3): δ = 149.0, 148.9, 142.3, 138.4,
132.1, 131.9, 131.8, 131.5, 131.2, 131.1, 130.0, 129.0,
128.9, 128.5, 128.3, 128.0, 127.9, 127.4, 126.2, 122.7,
120.5, 55.0 (d, JCP = 78.07 Hz), 51.3. 31P NMR
(CDCl3): δ = 31.96 (s). IR (neat): 3286 (NH), 1185
(P = O), 1067 (P-O) cm−1. HRMS Calcd for
C29H26N2OP (M + H)+ 449.1704. Found 449.1715.
Quinolin-2-yl-methyl(N-butylamino)diphenylphos-
phine Oxide (4c): White solid; yield 57%; mp
92–94◦C. 1H NMR (CDCl3): δ = 8.17 (d, 1H, Qu-4
J = 4.45 Hz), 7.88–7.33 (m, 15H, Qu-6, Qu-7, Qu-8,
Qu-3, Qu-9, and Phs), 5.12 (d, 1H, CH-P J =
12.69 Hz), 2.49–2.39 (m, 2H, CH2), 1.30–1.25 (m,
2H, CH2), 1.14–1.07 (m, 2H, CH2), 0.72–0.67 (m, 3H,
CH3).31P NMR (CDCl3): δ = 29.30 (s).
Quinolin-2-yl-methyl(N-benzylamino)phos-
phonic Acid (6b): White solid; yield 56%; mp 182–
1
186◦C. H NMR (D2O): δ = 8.32 (d, 1H, Qu-4 J =
8.52 Hz), 7.43–7.26 (m, 5H, Qu-6, Qu-7, Qu-8, Qu-3,
Qu-9), 6.90–6.60 (m, 5H, Ph), 4.08 (d, 1H, CH-P
J = 13.04 Hz), 3.82 (t, 2H, CH2Ph J = 5.99 Hz). 31P
NMR (D2O): δ = 3.55 (s).
Quinolin-3-yl-methyl(N-butylamino)phosphonic
Acid (6c): White solid; yield 55%; mp 190–196◦C.
1H NMR (D2O): δ = 8.92 (s, 1H, Qu-2 J = 4.96 Hz),
7.96–7.60 (m, 5H, Qu-6, Qu-7, Qu-8, Qu-9), 4.57 (d,
1H, CH-P J = 16.22 Hz), 2.82–2.66 (m, 2H, CH2),
1.37–1.33 (m, 2H, CH2), 0.96–0.89 (m, 2H, CH2),
0.49–0.44 (m, 3H, CH3). 31P NMR (D2O): δ = 7.56
(s). IR (neat): 3389 (NH), 1176 (P = O) cm−1. HRMS
Calcd for C14H20N2O3P(M + H)+ 295.1133. Found
295.1245.
Quinolin-3-yl-methyl(N-benzylamino)phospho-
nic Acid (6d): White solid; yield 53%; mp 168–172◦C.
1H NMR (D2O): δ = 9.13 (s, 1H, Qu-2), 9.06 (s, 1H,
Qu-4), 8.27–7.23 (m, 19H, Qu-6, Qu-7, Qu-8, Qu-9,
and Phs), 4.19 (d, 1H, CH-P J = 17.04 Hz), 4.43 (dd,
2H, CH2Ph J = 13.11 Hz). 31P NMR (D2O): δ = 7.55
(s). IR (neat): 3388 (NH), 1159 (P = O) cm−1. HRMS
Calcd for C17H18N2O3P (M + H)+ 329.0977. Found
329.1074.
Quinolin-2-yl-methyl(N-benzylamino)diphenyl-
phosphine Oxide (4d): White solid; yield 52%;
mp 98–104◦C. 1H NMR (DMSO-d6): δ = 8.20 (d,
1H, Qu-4 J = 8.49 Hz), 7.82–7.05 (m, 20H, Qu-6,
Qu-7, Qu-8, Qu-3, Qu-9, and Phs), 5.10 (dd, 1H,
CH-P J = 11.31 Hz), 3.72–3.46 (m, 2H, CH2Ph).
13C NMR (CDCl3): δ = 156.51, 149.5, 147.5, 136.1,
132.3, 132.2, 132.0, 131.9, 131.8, 131.7, 129.3, 129.0,
128.5, 128.3, 128.2, 128.0, 127.6, 127.1, 126.3, 126.2,
Quinolin-4-yl-methyl(N-butylamino)phosphonic
Acid (6e): White solid; yield 56%; mp 140–142◦C.
1H NMR (D2O): δ = 9.44 (d, 1H, Qu-2 J = 5.91 Hz),
3
121.9, 64.2 (d, JC-P = 78.37 Hz), 52.7 (d, JC-P
=
13.65 Hz). 31P NMR (DMSO-d6): δ = 30.14 (s). IR
Heteroatom Chemistry DOI 10.1002/hc