Nano Copper(0)-Stabilized on Alumina: Efficient and Recyclable Heterogeneous Catalyst for…
J=8.7 Hz, 2H), 6.97 (d, J=8.8 Hz, 2H), 6.85 (d, J=8.7 Hz,
2H), 5.38 (s, 2H), 3.85 (s, 3H), 3.78 (s, 3H); 13C NMR
(101 MHz, CDCl3) δ 160.9, 159.1, 154.1, 143.1, 136.1,
130.7, 128.5, 127.2, 122.7, 122.5, 119.7, 114.33, 114.0,
110.4, 55.3, 47.9 ; ESI-MS [M+H+]+: m/z=345; HRMS
(ESI orbitrap): calc. for C22H20N2O2 [M+H]+: 345.1597,
found: 345.1611.
4.1.9 1‑(2‑Nitrobenzyl)‑2‑(2‑nitrophenyl)‑1H‑benzo[d]
1
Yellow solid; H NMR (400 MHz, CDCl3) δ 8.15 (ddd,
J = 13.0, 7.2, 2.6 Hz, 2H), 7.86 (d, J = 7.9 Hz, 1H),
7.74–7.60 (m, 2H), 7.56–7.42 (m, 3H), 7.39–7.33 (m,
1H), 7.33–7.27 (m, 1H), 7.15 (d, J=7.9 Hz, 1H), 6.95 (d,
J=7.1 Hz, 1H), 5.69 (s, 2H); 13C NMR (126 MHz, CDCl3)
δ 149.8, 149.0, 147.0, 143.0, 134.8, 134.3, 133.1, 132.1,
131.5, 128.9, 128.4, 125.5, 125.27, 123.9, 123.2, 110.2,
45.7. ESI-MS [M + H]+: m/z = 375; HRMS (ESI orbit-
rap): calc. for C20H14N4O4 [M + H]+: 375.10878, found:
375.10951.
4.1.6 1‑(2,3‑Dimethoxybenzyl)‑2‑(2,3‑dimethoxyphenyl)‑1
H‑benzo[d]imidazole (3f)
Yellow solid (MP: 86–90 °C); 1H NMR (400 MHz, CDCl3)
δ 7.83 (d, J = 7.8 Hz, 2H), 7.30–7.23 (m, 5H), 7.22–7.17
(m, 2H), 7.16–7.13 (m, 4H), 7.07–7.02 (m, 2H), 6.82 (t,
J = 7.9 Hz, 2H), 6.76 (dd, J = 8.2, 1.3 Hz, 2H), 6.28 (dd,
J=7.6, 1.3 Hz, 2H), 5.34 (s, 4H), 3.91 (s, 6H), 3.82 (s, 6H),
3.65 (t, J = 5.7 Hz, 12H); 13C NMR (126 MHz, CDCl3)
δ 152.7, 152.5, 151.7, 147.5, 146.4, 143.2, 135.3, 130.0,
125.4, 124.5, 124.1, 123.8, 122.6, 122.0, 119.8, 114.0, 111.7,
110.9, 61.4, 60.4, 55.9, 55.72, 43.4; ESI-MS [M + H]+:
m/z = 405; HRMS (ESI orbitrap): calc. for C24H24N2O4
[M+H]+: 405.1808, found: 405.1809.
4.1.10 1‑(3‑Nitrobenzyl)‑2‑(3‑nitrophenyl)‑1H‑benzo[d]
1
Pale yellow solid; H NMR(300 MHz, CDCl3 + DMSO)
δ 8.52 (d, J = 1.9 Hz, 1H), 8.39–8.32 (m, 1H), 8.19 (d,
J=8.1 Hz, 1H), 8.11–8.00 (m, 2H), 7.89 (d, J=6.8 Hz, 1H),
7.72 (t, J=8.0 Hz, 1H), 7.58 (t, J=7.9 Hz, 1H), 7.45–7.29
(m, 4H), 5.65 (s, 2H); 13C NMR (75 MHz, CDCl3 +DMSO)
δ 151.0, 148.4, 142.8, 138.0, 135.8, 134.8, 131.8, 131.4,
130.3, 130.0, 124.6, 124.1, 124.0, 123.5, 123.2, 121.0,
120.4, 110.2, 47.6; ESI-MS [M + H]+: m/z = 375; HRMS
(ESI orbitrap): calc. for C20H14N4O4 [M+H]+: 375.10878,
found: 375.10954.
4.1.7 1‑(3,4,5‑Trimethoxybenzyl)‑2‑(3,4,5‑trimethoxypheny
l)‑1H‑benzo[d]imidazole (3g) [49]
White solid; 1H NMR (400 MHz, CDCl3) δ 7.91–7.84 (m,
1H), 7.37–7.34 (m, 1H), 7.34–7.28 (m, 2H), 6.92 (s, 2H),
6.36 (s, 2H), 5.40 (s, 2H), 3.89 (s, 3H), 3.82 (s, 3H), 3.72 (d,
J=1.2 Hz, 6H), 3.71 (s, 6H); 13C NMR (101 MHz, CDCl3)
δ 154.1, 154.0, 153.3, 142.8, 139.4, 137.4, 136.4, 132.5,
125.1, 123.2, 122.8, 119.9, 110.0, 106.3, 102.7, 60.89,
56.2, 56.0, 48.5; ESI-MS [M+H]+: m/z=465; HRMS (ESI
orbitrap): calc. for C26H28N2O6 [M+H]+: 465.2020, found:
465.2033, calc. for C26H28N2O6 [M+Na]+: 487.1839, found:
487.1852.
4.1.11 1‑(4‑Nitrobenzyl)‑2‑(4‑nitrophenyl)‑1H‑benzo[d]
1
White solid; H NMR (400 MHz, CDCl3) δ 8.33 (d,
J=8.9 Hz, 2H), 8.24 (d, J=8.8 Hz, 2H), 7.93 (d, J=7.9 Hz,
1H), 7.85 (d, J=8.8 Hz, 2H), 7.44–7.38 (m, 1H), 7.38–7.32
(m, 1H), 7.27 (d, J=9.3 Hz, 3H), 7.21 (d, J=7.9 Hz, 1H),
5.58 (s, 2H); 13C NMR (101 MHz, CDCl3) δ 148.5, 147.9,
143.1, 142.8, 135.7, 130.0, 126.7, 124.6, 124.1, 123.8,
120.8, 110.2, 48.0; ESI-MS [M + H]+: m/z = 375; HRMS
(ESI orbitrap): calc. for C20H14N4O4 [M+H]+: 375.10878,
found: 375.10947.
4.1.8 6‑Nitro‑1‑(3,4,5‑trimethoxybenzyl)‑2‑(3,4,5‑trimetho
xyphenyl)‑1H‑benzo[d]imidazole (3h)
1
Orange Solid (MP: 144–148 °C); H NMR (500 MHz,
CDCl3) δ 8.33–8.26 (m, 2H), 7.92 (d, J=9.0 Hz, 1H), 6.96
(s, 2H), 6.32 (s, 2H), 5.47 (d, J=17.1 Hz, 2H), 3.91 (s, 3H),
3.83 (s, 3H), 3.74 (s, 6H), 3.73 (s, 6H). 13C NMR (126 MHz,
CDCl3) δ 158.8, 154.1, 153.6, 147.4, 143.8, 140.4, 137.9,
135.8, 131.2, 123.8, 120.0, 118.9, 106.9, 106.5, 102.8, 60.9,
56.3, 56.0, 48.9. ESI-MS [M+H]+: m/z=510; HRMS (ESI
orbitrap): calc. for C26H27N3O8 [M + H]+ : 310.08223,
found: 310.08375.
4.1.12 1‑(4‑Fluorobenzyl)‑2‑(4‑fluorophenyl)‑1H‑benzo[d]
1
White solid; H NMR (500 MHz, CDCl3) δ 7.87 (d,
J = 7.9 Hz, 1H), 7.64 (dd, J = 7.9, 5.4 Hz, 2H), 7.32 (t,
J=7.5 Hz, 1H), 7.26 (t, J=7.4 Hz, 1H), 7.21 (d, J=7.9 Hz,
1H), 7.14 (t, J = 8.4 Hz, 2H), 7.02 (dd, J = 15.7, 7.2 Hz,
4H), 5.39 (s, 2H).; 13C NMR (101 MHz, CDCl3) δ 152.4,
143.1, 140.0, 135.9, 133.3, 131.8, 130.6, 129.5, 126.2,
125.9, 125.1, 123.9, 123.3, 122.4, 120.5, 110.3, 48.0; ESI-
MS [M+H]+: m/z=321; HRMS (ESI orbitrap): calc. for
C20H14F2N2 [M+H]+: 321.1197, found: 320.1198.
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