TAVAKOL AND KESHAVARZIPOUR
3 of 9
water and acetone and dried to afford the final catalyst
(MAG/IPS/DES).
2.5.3 | Ethyl 6‐amino‐4‐(4‐bromophenyl)‐5‐
cyano‐2‐methyl‐4H‐pyran‐3‐carboxylate (4 k)
Pale yellow solid; yield 92%; m.p. 174–175 °C. FT‐IR (KBr,
cm−1): 835, 1068, 1264, 1370, 1485, 1608, 1691, 2194,
2980, 3329, 3409. H NMR (400 MHz, CDCl3, δ, ppm):
2.5 | General procedure for preparation of 2‐
Amino‐4,6‐diphenyl‐4H‐pyran‐3‐carbonitrile
derivatives
1
1.14 (t, J = 7 Hz, 3H), 2.40 (s, 3H), 4.06 (m, 2H), 4.44 (s,
1H), 4.52 (s, 2H), 7.11 (d, J = 8 Hz, 2H), 7.45 (d,
J = 8 Hz, 2H). 13C NMR (125 MHz, CDCl3, δ, ppm): 13.9,
18.4, 38.4, 60.8, 105.6, 115.9, 118.5, 129.3, 131.7, 144.5,
157.5, 159.9, 160.2, 165.8. Anal. Calcd for C16H15N2O3Br
(%): C, 52.89; H, 4.13; N, 7.71. Found (%): C, 52.82; H,
4.19; N, 7.66.
Aldehyde (1 mmol) and malononirile (1 mmol) were added
to a 25 ml round‐bottomed flask containing MAG/IPS/DES
(0.1 g) and water (2 ml). The mixture was stirred for
30 min and ketone (1 mmol) was added. The resulting mix-
ture was stirred at room temperature. After completion of
the reaction (as monitored by TLC), the catalyst was removed
using a magnet, and then water (10 ml) was added. The water
layer was extracted with CH2Cl2 (3 × 30 ml), dried (MgSO4)
and concentrated. The product was purified by recrystalliza-
tion or TLC on 20 × 20 cm glass plate with hexane–EtOAc
(1:1 ratio) as solvent, or both. All products were known
compounds and their physical and spectroscopic data (m.p.,
2.5.4 | Ethyl 6‐amino‐4‐(4‐nitrophenyl)‐5‐cyano‐
2‐methyl‐4H‐pyran‐3‐carboxylate (4 l)
Pale yellow solid; yield 75%; m.p. 172–173 °C. FT‐IR (KBr,
cm−1): 850, 1059, 1173, 1270, 1345, 1519, 1608,1691, 2199,
2982, 3332, 3403. 1H NMR (400 MHz, CDCl3, δ, ppm): 1.13
(t, J = 7 Hz, 3H), 2.45 (s, 3H), 4.07 (q, J = 7 Hz, 2H), 4.57 (s,
2H), 4.59 (s, 1H), 7.40 (d, J = 8 Hz, 2H), 8.21 (d, J = 8 Hz,
2H). 13C NMR (125 MHz, CDCl3, δ, ppm): 14.0, 18.7, 38.8,
61.0, 106.8, 118.2, 124.1, 128.4, 151.0, 152.1, 153.1, 157.6,
158.1, 165.3. Anal. Calcd for C16H15N3O5 (%): C, 58.36; H,
4.56; N, 12.76. Found (%): C, 57.54; H, 3.00; N, 12.80.
1
FT‐IR, H NMR, 13C NMR and elemental analysis) were
compared with those of authentic samples in the litera-
ture.[39–42] The physical and spectroscopic data for selected
compounds are detailed below. Moreover, the images of
all analyses related to this products were shown in the
supporting informations.
2.5.1 | 2‐Amino‐4‐(4‐bromophenyl)‐6‐p‐tolyl‐
4H‐pyran‐3‐carbonitrile (4c)
3 | RESULTS AND DISCUSSION
White solid; yield 94%; m.p. 175–177 °C. FT‐IR (KBr, cm
First, the desired catalyst was prepared according to the
details presented in Section 1. The employed methodology
for this synthesis is shown in Scheme 1. After loading of
IPS on the surface of MAG via Fe─O─Si bonds, the
1
−1): 810, 1073, 1504, 1674, 2350, 2922, 3436. H NMR
(400 MHz, CDCl3, δ, ppm): 2.35 (s, 1H), 3.82–3.87 (m,
1H), 4.56 (d, J = 6.4 Hz, 1H), 7.18–7.27 (m, 5H), 7.48 (d,
J = 8 Hz, 1H), 7.77 (d, J = 9.2 Hz, 2H). 13C NMR
(100 MHz, CDCl3, δ, ppm):21.78, 28.59, 40.8, 111.49,
111.70, 123.40, 124.42, 128.23, 128.38, 129.04, 129.65,
129.72, 130.44, 131.91, 132.19, 132.52, 133.19, 135.51,
145.45.
2.5.2 | Ethyl 6‐amino‐4‐(4‐chlorophenyl)‐5‐
cyano‐2‐methyl‐4H‐pyran‐3‐carboxylate (4j)
Pale yellow solid; yield 94%; m.p. 169–170 °C. FT‐IR (KBr,
cm−1): 837, 1059, 1173, 1267, 1409, 1608, 1648, 1696,
1
2193, 2981, 3332, 3409. H NMR (400 MHz, CDCl3, δ,
ppm): 1.14 (t, J = 7 Hz, 3H), 2.40 (s, 3H), 4.06 (m, 2H),
4.46 (s, 1H), 4.49 (s, 2H), 7.16 (d, J = 8 Hz, 2H), 7.30 (d,
J = 8 Hz, 2H). 13C NMR (125 MHz, CDCl3, δ, ppm): 13.9,
18.5, 38.3, 60.8, 107.6, 118.6, 128.8, 128.9, 133.0, 142.3,
152.8, 157.1, 157.4, 165.6. Anal. Calcd for C16H15N2O3Cl
(%): C, 60.29; H, 4.71; N, 8.79. Found (%): C, 60.30; H,
4.75; N, 8.81.
SCHEME 1 Preparation of MAG/IPS/DES