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Z. Li et al.
Table 1 Phospha-Michael addition of various a,b-unsaturated malonates with diethyl phosphate catalyzed by MNPs@PA-IL
O
H
OEt
P
O
P
H
MNPs@PA-IL (10mol%)
OEt
Methanol, rt
EtO
H
CN
+
CN
R
EtO
R'
X
X
2
1
Entry
R
X
Reaction time (h)
Product
Yield (%)a
1
2
Ph
CN
CN
CN
CN
CN
CN
CN
CN
CN
CN
2
2a
2b
2c
2d
2e
2f
85
89
91
91
92
82
83
81
87
81
77
81
3-NO2–C6H4
4-NO2–C6H4
3-Cl–C6H4
4-Cl–C6H4
2-MeO–C6H4
3-MeO–C6H4
4-MeO–C6H4
4-Me–C6H4
2-Thienyl
2
3
2
4
1.5
1
5
6
3
7
3
2g
2h
2i
8
3
9
2.5
3
10
11
12
a
2j
Ph
CO2Et
CO2Et
5
2k
2l
4-MeO–C6H4
5
Isolated yield
b
Reaction conditions: a,b-unsaturated compounds (5.0 mmol), diethyl phosphate (5.0 mmol), MNPs@PA-IL (10 mol %), methanol (10 mL), rt
was purified with column chromatography using petroleum
ether/ethyl acetate as the eluent. The products were char-
1
acterized by H NMR and elemental analysis.
3H), 2.04 (s, 1H), 3.98–4.19 (m, 4H), 4.51–4.55 (m, 1H),
6.93 (d, J = 8.8 Hz, 2H), 7.39–7.42 (m, 2H). Anal. Calcd
for C14H16N3O5P: C, 49.86; H, 4.78; N, 12.46; O, 23.72; P,
9.18. Found: C, 49.82; H, 4.86; N, 12.41; O, 23.76; P, 9.15.
2.4.1 1H NMR Spectral and Elemental Analysis Data
of Products
2.4.1.4 diethyl 1-(3-chlorophenyl)-2,2-dicyanoethylpho-
sphonate (Table 1, Entry 4, 2d) [51] 1H NMR (400 MHz,
CDCl3): d 1.15 (t, J = 7.2 Hz, 3H), 1.40 (t, J = 7.2 Hz,
3H), 3.81–3.87 (m, 1H), 3.99–4.27 (m, 4H), 4.46–4.53 (m,
1H), 7.38–7.40 (m, 2H), 7.51–7.54 (m, 1H), 7.77–7.80 (m,
1H). Anal. Calcd for C14H16ClN2O3P: C, 51.47; H, 4.94;
Cl, 10.85; N, 8.57; O, 14.69; P, 9.48. Found: C, 51.41; H,
5.02; Cl, 10.83; N, 8.55; O, 14.76; P, 9.43.
2.4.1.1 diethyl
2,2-dicyano-1-phenylethylphosphonate
(Table 1, Entry 1, 2a) [51] 1H NMR (400 MHz, CDCl3):
d 1.14 (t, J = 7.2 Hz, 3H), 1.38 (t, J = 7.2z, 3H),
3.57–3.64 (m, 1H), 3.75–3.81 (m, 1H), 4.00–4.06 (m, 1H),
4.17–4.23 (m, 2H), 4.50–4.54 (m, 1H), 7.45–7.52 (m, 5H).
Anal. Calcd for C14H17N2O3P: C, 57.53; H, 5.86; N, 9.58;
O, 16.42; P, 10.60. Found: C, 57.49; H, 5.90; N, 9.55; O,
16.49; P, 10.57.
2.4.1.5 diethyl 1-(4-chlorophenyl)-2,2-dicyanoethylpho-
sphonate (Table 1, Entry 5, 2e) [51] 1H NMR (400 MHz,
CDCl3): d 1.14 (t, J = 6.8 Hz, 3H), 1.35 (t, J = 6.8 Hz,
3H), 2.03 (s, 1H), 3.98–4.19 (m, 4H), 4.51–4.55 (m, 1H),
6.93 (d, J = 8.8 Hz, 2H), 7.40 (d, J = 8.8 Hz, 2H). Anal.
Calcd for C14H16ClN2O3P: C, 51.47; H, 4.94; Cl, 10.85; N,
8.57; O, 14.69; P, 9.48. Found: C, 51.43; H, 4.99; Cl,
10.82; N, 8.52; O, 14.78; P, 9.46.
2.4.1.2 diethyl 2,2-dicyano-1-(3-nitrophenyl)ethylphosph-
onate (Table 1, Entry 2, 2b) [52] 1H NMR (400 MHz,
CDCl3): d 1.26 (t, J = 7.2 Hz, 3H), 1.39 (t, J = 7.2 Hz,
3H), 3.74–3.81 (m, 1H), 3.99–4.27 (m, 4H), 4.63–4.68 (m,
1H), 7.70 (t, J = 8.0 Hz, 1H), 7.90–7.92 (m, 1H), 8.33 (d,
J = 8.4 Hz, 1H), 8.40–8.41 (m, 1H). Anal. Calcd for
C14H16N3O5P: C, 49.86; H, 4.78; N, 12.46; O, 23.72; P,
9.18. Found: C, 49.80; H, 4.83; N, 12.45; O, 23.76; P, 9.16.
2.4.1.6 diethyl
2,2-dicyano-1-(2-methoxyphenyl)ethyl-
phosphonate (Table 1, Entry 6, 2f) [53] 1H NMR
(400 MHz, CDCl3): d 1.13 (t, J = 7.2 Hz, 3H), 1.33 (t,
J = 7.2 Hz, 3H), 2.04 (s, 1H), 3.81 (s, 3H), 3.98–4.19 (m,
4H), 4.51–4.54 (m, 1H), 6.95 (d, J = 8.8 Hz, 2H),
2.4.1.3 diethyl 2,2-dicyano-1-(4-nitrophenyl)ethylphosph-
onate (Table 1, Entry 3, 2c) [51] 1H NMR (400 MHz,
CDCl3): d 1.14 (t, J = 7.2 Hz, 3H), 1.35 (t, J = 7.2 Hz,
123