1
4
(C-4, JC-4,H-4 = 185.0); 125.0 (C-o); 129.78 (C-m); 135.54 (C-ipso, JC-ipso,H-4 ~1.0); 139.50 (C-p); 142.31 (C-5,
2JC-5,H-4 = 7.4, JC-5,Me = 7.9); 155.70 (C-3, JC-3,H-4 ~3.0). Mass spectrum, m/z (Irel, %): 217 [M]+ (100), 170
[M-HNO2]+ (10), 156 [M-NO-HCN]+ (60), 91 [C7H7]+ (28). Found, %: C 60.80; H 5.08; N 19.30. C11H11N3O2.
Calculated, %: C 60.82; H 5.10; N 19.34.
2
2
5-Methyl-3-nitro-1-phenyl-1H-pyrazole (2c). Yield 85%; mp 93-95oC (lit. mp 92-95oC [39]). 1H NMR
spectrum, δ, ppm (J, Hz): 2.38 (3H, d, 4J = 0.81, 5-CH3); 6.82 (1H, q, J = 0.81, H-4); 7.47 (2H, m, H-o); 7.49
4
(1H, m, H-p); 7.52 (2H, m, H-m). 13C NMR spectrum, δ, ppm (J, Hz): 13.51 (5-CH3); 103.71 (C-4,
1JC-4,H-4 = 185.5); 126.32 (C-o); 130.35 (C-m); 130.37 (C-p); 139.10 (C-ipso, JC-ipso,H-4 ~0.5); 143.26 (C-5,
4
2JC-5,H-4 = 7.6, JC-5,Me = 7.7); 156.99 (C-3, JC-3,H-4 ~2.0). Mass spectrum, m/z (Irel, %): 203 [M]+ (100), 186
2
2
[M-OH]+ (15), 156 [M-HNO2]+ (22), 142 [M-HN2O2]+, 77 [Ph] (37).
3,5-Dimethyl-1-(4-methylphenyl)-4-nitro-1H-pyrazole (3a). Yield 52%; mp 119-121oC. H NMR
1
spectrum, δ, ppm: 2.44 (3H, s, CH3 p-Tol); 2.59 (3H, s, 3-CH3); 2.61 (3H, s, 5-CH3); 7.27 (2H, m, H-o); 7.32
(2H, m, H-m). 13C NMR spectrum, δ, ppm (J, Hz): 12.78 (5-CH3); 13.98 (3-CH3); 21.18 (CH3 p-Tol); 125.48
2
(C-o); 130.03 (C-m); 132.08 (C-4); 135.45 (C-ipso); 139.60 (C-p); 140.80 (C-5, JC-5,Me = 7.6); 146.77 (C-3,
2JC-3,Me = 7.6). Found, %: C 62.43; H 5.55; N 18.03. C12H13N3O2. Calculated, %: C 62.33; H 5.67; N 18.17.
3,5-Dimethyl-4-nitro-1-phenyl-1H-pyrazole (3c). Yield 68%; mp 103-105oC (lit. mp 103-105oC [40]).
1H NMR spectrum, δ, ppm : 2.56 (3H, s, 3-CH3); 2.60 (3H, s, 5-CH3); 7.38 (2H, m, H-o); 7.46 (1H, m, H-p); 7.50
(2H, m, H-m). 13C NMR spectrum, δ, ppm (J, Hz): 12.78 (5-CH3); 13.98 (3-CH3); 125.54 (C-o); 129.23 (C-p);
2
2
129.36 (C-m); 132.06 (C-4); 137.81 (C-ipso); 140.70 (C-5, JC-5,Me = 7.9); 146.71 (C-3, JC-3,Me = 8.2). Mass
spectrum, m/z (Irel, %): 217 [M]+ (100), 200 [M-OH]+ (10), 170 [M-HNO2]+ (14), 132 [M-MeC2NO2]+, 118 [M-
HNO2-C4H4]+ (61), 104 [PhNCH]+ (31), 77 [Ph] (79).
4-Nitro-1-phenyl-1H-imidazole (4c). Yield 76%; mp 187oC (lit. mp 186-187oC [37]). 1H NMR spectrum,
δ, ppm (J, Hz): 7.47 (1H, m, H-p); 7.53 (2H, m, H-m); 7.71 (2H, m, H-o); 8.26 (1H, s, H-2); 8.62 (1H, d, 2J = 0.61,
H-5). 13C NMR spectrum, δ, ppm: 119.84 (C-o); 125.81 (C-5); 128.67 (C-p); 129.85 (C-m); 136.70 (C-2); 137.35
(C-4); 138.70 (C-ipso). Mass spectrum, m/z (Irel, %): 189 [M]+ (100), 104 [PhNHCN]+ (64), 77 [Ph] (60).
1
3-Nitro-1-phenyl-1H-pyrazole (5c). Yield 89%; mp 127oC (lit. mp 126-128oC [41]). H NMR
spectrum, δ, ppm (J, Hz): 7.10 (1H, d, 3J = 2.61, H-4); 7.43 (1H, m, H-p); 7.52 (2H, m, H-m); 7.75 (2H, m, H-o);
3
1
2
7.98 (1H, d, J = 2.61, H-5). 13C NMR spectrum, δ, ppm: 104.33 (C-4, JC-4,H-4 = 188.0, JC-4,H-5 = 8.4); 120.08
(C-o); 128.67 (C-p); 129.49 (C-5, 1JC-5,H-5 = 192.0, 2JC-5,H-4 = 8.2); 129.77 (C-m); 138.87 (C-ipso, 4JC-ipso,H-4 ~1.0,
3JC-ipso,H-5 ~1.0); 157.07 (C-3, JC-3,H-4 = 2.0, JC-3,H-5 = 10.2). Mass spectrum, m/z (Irel, %): 189 [M]+ (100), 142
2
3
[M-HNO2]+ (21), 77 [Ph] (60).
2,4-Dinitro-1-phenyl-1H-imidazole (6c). Yield 57%; mp 164oC. 1H NMR spectrum, δ, ppm: 7.41 (2H,
m, H-o); 7.60 (2H, m, H-m); 7.64 (1H, m, H-p); 7.96 (1H, s, H-5). 13C NMR spectrum, δ, ppm: 123.72 (C-5);
125.43 (C-o); 130.12 (C-m); 131.13 (C-p); 134.97 (C-ipso); 140.91 (C-4); 143.93 (C-2). Mass spectrum, m/z,
(Irel, %): 234 [M]+ (9), 130 [M+H-PhNCN]+ (23), 115 [M+H-PhNCO]+ (20), 77 [Ph] (100). Found, %: C 46.10;
H 2.51; N 23.81. C9H6N4O4. Calculated, %: C 46.16; H 2.58; N 23.92.
1
3-Nitro-1-phenyl-1H-1,2,4-triazole (7c). Yield 46%; mp 133oC (lit. mp 132oC [42]). H NMR
spectrum, δ, ppm: 7.51 (1H, m, H-p); 7.57 (2H, m, H-m); 7.74 (2H, m, H-o); 8.65 (1H, s, H-5). 13C NMR
spectrum, δ, ppm: 120.47 (C-o); 130.00 (C-p); 130.12 (C-m); 135.69 (C-ipso); 142.30 (C-5); 163.25 (C-3). Mass
spectrum, m/z (Irel, %): 190 [M]+ (100), 117 [M-HCN-NO2]+ (16), 77 [Ph] (42).
The work was carried out with the support of the Russian Fund for Fundamental Investigations (grant
09-03-00779).
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