RSC Advances
Page 12 of 14
DOI: 10.1039/C5RA16289K
126.7, 128.9, 129.2, 129.3, 129.9, 131.3, 134.1, 138.1,
140.2, 145.7.
1653, 1593, 1518, 1398 cmꢀ1; 1H NMR (400 MHz, DMSOꢀ
d6): δppm 1.77 (s, 3H, —CH3), 4.89 (s, 1H, —CH), 7.33 (d, 60
4H, J = 8.0 Hz, ArH), 7.53 (t, 5H, J = 8.4 Hz, ArH), 7.86
(d, 2H, J = 8.0 Hz, ArH), 7.90 (s, 1H, ArH), 7.92 (s, 2H,
—NH2); 13C NMR (100 MHz, DMSOꢀd6): δppm 35.2, 37.5,
58.5, 124.9, 125.1, 125.2, 125.3, 125.4, 126.5, 126.6,
126.7, 126.8, 127.7, 1238.0, 128.1, 131.1, 131.2, 131.3, 65
133.4, 133.8, 134.0, 139.8, 142.9, 143.8.
6ꢀAminoꢀ3ꢀmethylꢀ1ꢀphenylꢀ4ꢀ(1ꢀphenylpropꢀ1ꢀenꢀ2ꢀyl)ꢀ1,4ꢀ
dihydropyrano[2,3ꢀc]pyrazoleꢀ5ꢀcarbonitrile (Table 4,
o
entry 4): Yellow solid; M.p: 267ꢀ269 C; Yield: 89%; IR
5
(KBr): υ 3545, 3470, 3414, 3333, 3061, 2925, 2204, 1599,
1499, 1383 cmꢀ1; 1H NMR (400 MHz, DMSOꢀd6): δppm
1.87 (s, 3H, —CH3), 2.10 (s, 3H, —CH3), 6.41 (s, 1H, —
CH), 6.84 (s, 1H, —CH), 7.06 (d, 2H, J = 7.2 Hz, ArH),
7.32 (t, 6H, J = 7.6 Hz, ArH), 7.96 (d, 2H, J = 7.2 Hz, 10
ArH), 8.04 (s, 2H, —NH2); 13C NMR (100 MHz, DMSOꢀ
d6): δppm 21.1, 37.4, 69.4, 101.2, 111.7, 116.2, 122.9,
123.1, 125.3, 125.5, 125.6, 125.7, 126.1, 126.4, 126.6,
127.0, 128.1, 129.4, 131.1, 134.0, 138.4, 139.4, 145.9,
6ꢀAminoꢀ4ꢀ(3,4ꢀdihydroxyphenyl)ꢀ3ꢀmethylꢀ1ꢀphenylꢀ1,4ꢀ
dihydropyrano[2,3ꢀc]pyrazoleꢀ5ꢀcarbonitrile (Table 4,
o
entry 10): Orange solid; M.p: 189ꢀ191 C; Yield: 88%; IR
(KBr): υ 3413, 3329, 3237, 2186, 1655, 1598, 1496, 1384 70
1
cmꢀ1; H NMR (400 MHz, DMSOꢀd6): δppm 1.90 (s, 3H, —
CH3), 4.14 (s, 1H, —OH), 4.49 (s, 1H, —OH), 6.58 (d,
1H, J = 8.4 Hz, ArH), 6.71 (d, 1H, J = 8.0 Hz, ArH), 6.83
(s, 1H, —CH), 6.86 (s, 1H, ArH), 7.10 (t, 1H, J = 6.8 Hz,
ArH), 7.16 (s, 2H, —NH2), 7.33 (t, 1H, J = 7.6 Hz, ArH), 75
7.51 (t, 1H, J = 8.0 Hz, ArH), 7.81 (d, 1H, J = 7.6 Hz,
ArH), 7.90 (d, 1H, J = 7.6 Hz, ArH); 13C NMR (100 MHz,
DMSOꢀd6): δppm 33.8, 36.6, 59.4, 99.6, 115.3, 115.5,
118.4, 119.1, 120.1, 120.3, 124.2, 126.6, 128.9, 129.9,
152.2.
15
6ꢀAminoꢀ4ꢀ(2ꢀhydroxyꢀ3ꢀmethoxyphenyl)ꢀ3ꢀmethylꢀ1ꢀphenylꢀ
1,4ꢀdihydropyrano[2,3ꢀc]pyrazoleꢀ5ꢀcarbonitrile (Table 4,
entry 5): Pink solid; M.p: 297ꢀ299 oC; Yield: 90%; IR
(KBr): υ 3462, 3420, 3333, 3231, 3062, 2945, 2201, 1640,
1599, 14971361 cmꢀ1; 1H NMR (400 MHz, DMSOꢀd6): 20
δppm 1.86 (s, 3H, —CH3), 2.09 (s, 3H, —CH3), 3.82 (s, 1H,
—OH), 3.98 (s, 1H, —CH), 6.88 (d, 4H, J = 8.0 Hz, ArH),
7.30 (t, 2H, J = 7.8 Hz, ArH), 7.51 (s, 2H, —NH2), 7.91 (t,
2H, J = 6.8 Hz, ArH); 13C NMR (100 MHz, DMSOꢀd6):
δppm 21.1, 32.6, 37.2, 60.3, 100.4, 100.5, 101.4, 111.4, 25
116.0, 116.1, 126.1, 126.2, 126.7, 126.9, 127.5, 128.9,
129.3, 129.5, 137.3, 137.6, 140.8, 140.9, 145.0.
138.1, 145.9, 146.6, 157.7, 159.6.
80
6ꢀAminoꢀ3ꢀmethylꢀ1ꢀphenylꢀ4ꢀ(pyridinꢀ4ꢀyl)ꢀ1,4ꢀ
dihydropyrano[2,3ꢀc]pyrazoleꢀ5ꢀcarbonitrile (Table 4,
entry 12): Red solid; M.p: 249ꢀ251 oC; Yield: 88%; IR
(KBr): υ 3406, 3346, 3152, 3066, 2919, 2195, 1667, 1595,
1520, 1395 cmꢀ1; 1H NMR (400 MHz, DMSOꢀd6): δppm 85
1.82 (s, 3H, —CH3), 4.78 (s, 1H, —CH), 7.36 (d, 1H, J =
6.6 Hz, ArH), 7.41 (s, 2H, —NH2), 7.51 (t, 3H, J = 8.0 Hz,
ArH), 7.65 (d, 1H, J = 8.8 Hz, ArH), 7.81 (d, 2H, J = 7.6
Hz, ArH), 8.57 (d, 2H, J = 7.0 Hz, ArH); 13C NMR (100
MHz, DMSOꢀd6): δppm 30.6, 41.3, 57.9, 123.4, 124.2, 90
125.0, 125.4, 128.2, 128.3, 128.4, 129.3, 129.8, 130.0,
131.6, 133.6, 134.1, 134.6, 142.6, 145.4.
6ꢀAminoꢀ4ꢀ(3ꢀethoxyꢀ4ꢀhydroxyphenyl)ꢀ3ꢀmethylꢀ1ꢀphenylꢀ
1,4ꢀdihydropyrano[2,3ꢀc]pyrazoleꢀ5ꢀcarbonitrile (Table 4,
o
entry 6): Orange solid; M.p: 175ꢀ177 C; Yield: 89%; IR 30
(KBr): υ 3420, 3331, 3229, 3195, 2984, 2186, 1647, 1597,
1516, 1494, 1395 cmꢀ1; 1H NMR (400 MHz, DMSOꢀd6):
δppm 1.32 (t, 3H, J = 7.0 Hz, —CH3), 1.84 (s, 3H, —CH3),
4.02 (q, 2H, J = 6.8 Hz, —CH3), 4.58 (s, 1H, —OH), 6.44
(d, 1H, J = 8.0 Hz, ArH), 6.78 (d, 1H, J = 8.0 Hz, ArH), 35 Computational detail
6.82 (s, 1H, —CH), 7.07 (t, 1H, J = 7.4 Hz, ArH), 7.17 (s,
1H, ArH), 7.30 (t, 1H, J = 7.2 Hz, ArH), 7.50 (t, 1H, J =
8.0 Hz, ArH), 7.82 (d, 1H, J = 8.0 Hz, ArH), 7.89 (d, 1H,
J = 7.6 Hz, ArH), 8.08 (s, 2H, —NH2); 13C NMR (100
MHz, DMSOꢀd6): δppm 27.0, 34.5, 36.8, 59.1, 64.3, 119.4, 40
120.1, 120.3, 120.7, 120.8, 124.1, 126.5, 128.9, 129.4,
129.8, 135.0, 138.1, 144.2, 145.0, 145.9, 146.3, 146.4.
6ꢀAminoꢀ3ꢀmethylꢀ4ꢀ(3ꢀnitrophenyl)ꢀ1ꢀphenylꢀ1,4ꢀ
Computations were performed using the Gaussian09
program.42 Density functional theory has been used to 95
investigate the reactions of 5ꢀaminoꢀpyrazoleꢀ4ꢀ
carbonitrile derivatives (5) in the presence of
{[HMIM]C(NO2)3} as
a
nanostructure ionic liquid
catalyst. All geometry optimizations were performed at
B3LYP/TZVP level of theory and frequency calculations 100
were carried out at the same level. All frequencies in the
nonꢀtransition states are real. We have used the corrected
electronic energy and Gibbs free energy for investigation
of the mechanism of the synthesis of 5ꢀaminoꢀpyrazoleꢀ4ꢀ
carbonitrile derivatives (5). The nature of transition 105
structure was confirmed by intrinsic reaction coordinate
(IRC)43 searches and vibrational frequency calculations.
The intramolecular interactions were calculated on the
basis of natural bond orbital (NBO)44 analyses.
dihydropyrano[2,3ꢀc]pyrazoleꢀ5ꢀcarbonitrile (Table 4,
o
entry 7): Yellow solid; M.p: 207ꢀ209 C; Yield: 93%; IR 45
(KBr): υ 3462, 3411, 3328, 3249, 3195, 3057, 2920, 2195,
1661, 1597, 1519, 1385 cmꢀ1; 1H NMR (400 MHz, DMSOꢀ
d6): δppm 1.82 (s, 3H, —CH3), 4.80 (s, 1H, —CH), 7.35 (d,
2H, J = 7.2 Hz, ArH), 7.42 (s, 1H, ArH), 7.52 (t, 2H, J =
8.0 Hz, ArH), 7.69 7.30 (t, 2H, J = 7.6 Hz, ArH), 7.83 (d, 50
2H, J = 7.6 Hz, ArH), 8.18 (s, 2H, —NH2); 13C NMR (100
MHz, DMSOꢀd6): δppm 13.4, 26.6, 36.7, 57.5, 119.2,
119.8, 120.3, 120.6, 120.8, 122.3, 122.7, 122.8, 123.2,
123.9, 126.8, 128.9, 129.4, 129.7, 129.8, 130.8, 134.9.
Acknowledgements
110
We thank BuꢀAli Sina University and Iran National Science
Foundation (INSF) for financial support to our research
group.
6ꢀAminoꢀ3ꢀmethylꢀ4ꢀ(naphthalenꢀ2ꢀyl)ꢀ1ꢀphenylꢀ1,4ꢀ
55
dihydropyrano[2,3ꢀc]pyrazoleꢀ5ꢀcarbonitrile (Table 4,
o
entry 9): Yellow solid; M.p: 206ꢀ209 C; Yield: 93%; IR
(KBr): υ 3554, 3441, 3351, 3301, 3191, 3095, 2925, 2191,
Notes and references
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