V. Montoya et al. / Tetrahedron 61 (2005) 12377–12385
12383
3J3–2,4Z8.0 Hz, 1H, H-3), 7.99 (d, 3J4–3Z8.0 Hz, 1H, H-4),
8.65 (d, 3J1–2Z5.0 Hz, 1H, H-1). 13C{1H} NMR (63 MHz,
25 8C, CDCl3): dZ14.3 (pz-(CH2)7–CH3), 22.9–30.8 (pz-
CH2–CH2–(CH2)5), 32.0 (pz-CH2–CH2), 50.2 (pz-CH2),
105.0 (C-5), 122.5 (C-2), 128.8–129.2 (CPh, C-3), 120.3
(C-4), 150.0 (C-1), 131.2 (C-60), 145.3, 150.9, 152.8 (C-6,
C-7, C-8) ppm.
139.0, 150.3 (C-6, C-7, C-8) ppm. (L1b0) 1H NMR
(250 MHz, 25 8C, CDCl3 solution): dZ1.41 (t, 3JZ
7.0 Hz, 3H, pz-CH2–CH3), 2.33 (s, 1H, pz-CH3), 4.11 (q,
3JZ7.0 Hz, 2H, pz-CH2–CH3), 6.07 (s, 1H, H-5), 7.39–7.49
(m, 5H, H-1, H-2, H-3, H-4, H-10) ppm. 13C{1H} NMR
(63 MHz, 25 8C, CDCl3): dZ13.8 (pz-CH3), 16.2 (pz-CH2–
CH3), 44.4 (pz-CH2–CH3), 105.9 (C-5) 128.6 (C-2), 128.9–
129.0 (C-1, C-3, C-4, C-10), 131.6, 144.6, 147.9 (C6, C7, C8)
ppm.
4.3.3. 2-(5-Methyl-1-octyl-1H-pyrazol-3-yl)-pyridine
(L3a). C17H25N3 (271.2) calcd: C, 75.23; H, 9.28; N,
15.48, found C, 75.20; H, 9.52; N, 16.08%. IR (NaCl, cmK1) n
(C–H)ar 3061, n (C–H)al 2925, n ((C]N), (C]C))ar 1606,
1551, d ((C]N), (C]C))ar 1456, 1441, d (C–H)ar,oop 786,
762. MS (ESI): m/z (%)Z294.2 [MNaC] (54%), 272.2
[MHC] (100%). 1H NMR (250 MHz, 25 8C, CDCl3
solution): dZ0.87 (t, 3JZ7.0 Hz, 3H, pz-(CH2)7–CH3),
1.26–1.31 (m, 10H, pz-CH2–CH2–(CH2)5), 1.83–1.90 (m,
4.3.6. 2-(1-Ethyl-5-phenyl-1H-pyrazol-3-yl)-pyridine
(L2b)/2-(2-ethyl-5-phenyl-1H-pyrazol-3-yl)-pyridine
(L2b0). C16H15N3 (249.1): calcd C, 77.11; H, 6.02; N, 16.87,
found C, 77.18; H, 5.84; N, 16.15%. IR (NaCl, cmK1) n
(C–H)ar 3052, n (C–H)al 2975, n ((C]N), (C]C))ar 1595,
1567, d ((C]N), (C]C))ar 1475, d (C–H)ar,oop 788, 766.
MS (ESI): m/z (%)Z272.1 [MNaC] (46%), 250.1 [MHC]
3
1
2H, pz-CH2–CH2), 2.33 (s, 3H, pz-CH3), 4.07 (t, 2H, JZ
(100%), 222.0 [MHCKCH2CH3] (3%). (L2b) H NMR
7.3 Hz, pz-CH2), 6.62 (s, 1H, H-5), 7.15 (dd, 3J2–3Z7.3 Hz,
(250 MHz, 25 8C, CDCl3): dZ1.41 (t, JZ7.0 Hz, 3H, pz-
3
3
3
3J2–1Z4.8 Hz, 1H, H-2), 7.63 (dd J2–3Z7.3 Hz, J3–4
Z
Z
CH2–CH3), 4.19 (q, 3JZ7.0 Hz, 2H, pz-CH2–CH3), 6.87 (s,
3
3
8.1 Hz, 1H, H-3), 7.89 (dt, 1H, J4–3Z8.1 Hz, J4–2,1
1H, H-5), 7.13 (t, J2–1,3Z5.0 Hz, 1H, H-2), 7.40 (m, 5H,
1.1 Hz, H-4), 8.60 (d, 1H, J1–2Z4.8 Hz, H-1). 13C{1H}
NMR (63 MHz, 25 8C, CDCl3): dZ11.3 (pz-CH3), 14.1 (pz-
(CH2)7–CH3), 22.7, 26.8, 29.2, 29.3, 30.5 (pz-CH2–CH2–
(CH2)5), 31.8 (pz-CH2–CH2), 49.5 (pz-CH2), 104.0 (C-5),
122.1 (C-2), 136.5 (C-3), 139.4 (C-8), 149.4 (C-1), 150.1
(C-7), 152.8 (C-6) ppm.
HPh), 7.66 (t, J3–2,4Z8.0 Hz, 1H, H-3), 7.93 (d, J4–3Z
3
3
3
3
8.0 Hz, 1H, H-4), 8.60 (d, J1–2Z5.0 Hz, 1H, H-1) ppm.
13C{1H} NMR (63 MHz, 25 8C, CDCl3): dZ15.7 (pz-CH2–
CH3), 44.7 (pz-CH2–CH3), 104.6 (C-5), 119.8 (C-4), 122.1
(C-2), 128.6 (CPh), 136.3 (C-3), 149.2 (C-1), 130.5, 144.5,
1
150.5, 152.2 (C-6, C-7, C-8, C-60) ppm. (L2b0) H NMR
3
(250 MHz, 25 8C, CDCl3): dZ1.51 (t, JZ7.0 Hz, 3H, pz-
CH2–CH3), 4.19 (q, 3JZ7.0 Hz, 2H, pz-CH2–CH3), 6.88 (s,
4.3.4. 2-(1-Octyl-5-trifluoromethyl-1H-pyrazol-3-yl)-
pyridine (L4a). C17H22N3F3 (325.2) calcd: C, 62.75; H,
6.81; N, 12.91, found C, 62.72; H, 7.28; N, 13.39%. IR
(NaCl, cmK1) n (C–)ar 3063, n (C–)al 2960, n ((C]N),
(C]C))ar 1596, 1569, d ((C]N), (C]C))ar 1456, 1416, n
(C–H) 1274, d (C–H)ar,oop 789, d (C–H) 743. MS (ESI): m/z
(%)Z348.2 [MNaC] (20%), 326.2 [MHC] (100%). 1H
1H, H-5), 7.26 (m, 1H, H-2), 7.33 (t, 3J2 –1 ,3 Z7.0 Hz, 1H,
0
0
0
3
H-20), 7.44 (m, 2H, H-10, H-30), 7.89 (d, J10 ,4 –3 ,1
Z
0
0
0
0
7.0 Hz, 2H, H-100, H-40), 7.77 (t, 3J3–2,4Z8.0 Hz, 1H, H-3),
3
3
7.64 (d, J4–3Z8.0 Hz, 1H, H-4), 8.70 (d, J1–2Z5.0 Hz,
1H, H-1) ppm. 13C{1H} NMR (63 MHz, 25 8C, CDCl3): dZ
16.4 (pz-CH2–CH3), 46.9 (pz-CH2–CH3), 104.0 (C-5),
122.8 (C-2), 123.2 (C-4) 126.0 (C-40, C-100), 127.9 (C-20),
129.0 (C-10, C-30), 137.0 (C-3), 149.7 (C-1), 133.9, 142.3,
150.4, 150.5 (C-6, C-7, C-8, C-60) ppm.
3
NMR (250 MHz, 25 8C, CDCl3 solution): dZ0.89 (t, JZ
7.0 Hz, 3H, pz-(CH2)7–CH3), 1.28–1.39 (m, 10H, pz-CH2–
CH2–(CH2)5), 1.93–1.98 (m, 2H, pz-CH2–CH2), 4.26 (t, 2H,
3JZ7.0 Hz, pz-CH2–CH2–(CH2)5), 7.20–7.28 (m, 1H, H-2),
7.24 (s, 1H, H-5), 7.73 (t, 3J3–2,4Z7.0 Hz, 1H, H-3), 7.95 (d,
4.3.7. 2-(1-Ethyl-5-methyl-1H-pyrazol-3-yl)-pyridine
(L3b). C11H13N3 (187.0) calcd: C, 70.56; H, 7.00; N,
22.44, found C, 70.17; H, 7.34; N, 23.18%. IR (NaCl, cmK1) n
(C–H)ar 3061, n (C–H)al 2979, n ((C]N), (C]C))ar 1592,
1566, d ((C]N), (C]C))ar 1499, d (C–H)ar,oop 785. MS
(ESI): m/z (%)Z210.0 [MNaC] (100%), 188.0 [MHC]
3
3J4–3Z8.0 Hz, 1H, H-4), 8.64 (d, J1–2Z5.0 Hz,1H, H-1),
13C{1H} NMR (63 MHz, 25 8C, CDCl3): dZ14.4 (pz-
(CH2)7–CH3), 23.0, 26.9, 29.4, 29.5, 30.7 (pz-CH2–CH2–
(CH2)5), 32.1 (pz-CH2–CH2), 52.0 (pz-CH2), 106.2 (q,
1
3JC,FZ2.4 Hz, C-5), 120.4 (C-4), 120.5 (q, JC,F
Z
2
1
268.7 Hz, CF3), 123.3 (C-2), 133.4 (q, JC,FZ39.3 Hz,
C-8), 137.1 (C-3), 149.9 (C-1), 151.0, 151.5 (C-6, C-7) ppm.
(31%). H NMR (250 MHz, 25 8C, CDCl3 solution): dZ
3
1.46 (t, JZ7.0 Hz, 3H, pz-CH2–CH3), 2.33 (s, 3H, pz-
3
CH3), 4.16 (q, 2H, JZ7.0 Hz, pz-CH2–CH3), 6.62 (s, 1H,
3
3
4
H-5), 7.15 (ddd, J2–3Z8.0 Hz, J2–1Z4.0 Hz, J2–4
Z
4.3.5. 1-Ethyl-5-methyl-3-phenyl-1H-pyrazole (L1b)/
2-ethyl-5-methyl-3-phenyl-1H-pyrazole (L1b0). C12H14N2
(186.0): calcd C, 77.42; H, 7.53; N, 15.05, found C, 77.43;
H, 7.96; N, 14.64%. IR (NaCl, cmK1) n (C–)ar 3061, n (C–)al
2935, n ((C]N), (C]C))ar 1605, 1552, d ((C]N),
(C]C))ar 1455, 1440 d (C–)ar,oop 796, 765. MS (ESI): m/z
(%)Z209.0 [MNaC] (50%), 187.0 [MHC] (100%). (L1b)
3
4
1.0 Hz, 1H, H-2), 7.68 (td, J3–2,4Z7.0 Hz, J3–1Z2Hz,
1H, H-3), 7.88 (d, 3J4–3Z8.0 Hz, 1H, H-4), 8.61 (d, 3J1–2
Z
5.0 Hz, 1H, H-1), 13C{1H} NMR (63 MHz, 25 8C, CDCl3):
dZ11.5 (pz-CH3), 15.9 (pz-CH2–CH3), 44.6 (pz-CH2–
CH3), 104.4 (C-5), 120.2 (C-4), 122.4 (C-2), 136.8 (C-3),
139.4 (C-8), 149.8 (C-1), 150.5 (C-7), 153.0 (C-6).
3
1H NMR (250 MHz, 25 8C, CDCl3): dZ1.47 (t, JZ7 Hz,
3H, pz-CH2–CH3), 2.33 (s, 1H, pz-CH3), 4.15 (q, 3JZ
7.0 Hz, 2H, pz-CH2–CH3), 6.33 (s, 1H, H-5), 7.29 (t,
4.3.8. 2-(1-Ethyl-5-trifluoromethyl-1H-pyrazol-3-yl)-
pyridine (L4b). C11H10N3F3 (241.0): calcd: C, 54.77; H,
4.15; N, 17.43, found C, 54.32; H, 4.36; N, 17.85%. IR
(NaCl, cmK1) n (C–H)ar 3061, n (C–H)al 2962, n ((C]N),
(C]C))ar 1597, 1558, d ((C]N), (C]C))ar 1448, 1417, d
(C–H)ar,oop 788. MS (ESI): m/z (%)Z264.0 [MNaC] (3%),
3
3J3–2,4Z7.0 Hz, 1H, H-2), 7.40 (t, J10,4–1,3Z7.0 Hz, 2H,
3
H-10, H-4), 7.80 (d, J1,3–2Z7.0 Hz, 2H, H-1, H-3),
13C{1H} NMR (63 MHz, 25 8C, CDCl3): dZ11.4 (pz-
CH3), 15.8 (pz-CH2–CH3), 44.3 (pz-CH2–CH3), 102.9 (C-5)
127.6 (C-2), 125.8 (C-1, C-3), 128.8 (C-10, C-4), 134.3,
1
242.0 [MHC] (100%), 214.0 [MHCKCH2CH3] (3%). H