N. Zohreh, A. Alizadeh / Tetrahedron 67 (2011) 4595e4600
4599
(KBr) (nmax, cmꢀ1): 1766 (C]O), 1732 (C]O), 1590 and 1452 (Ar),
1228 and 1166 (CeO), 766 (CeCl). Anal. Calcd for C18H13ClN2O4
(356.76): C, 60.60; H, 3.67; N, 7.85%. Found: C, 60.65; H, 3.66; N,
7.82%. MS (EI, 70 eV): m/z (%)¼356.76 (Mþ, 6), 325 (10), 218 (8), 140
(98), 139 (100), 111 (14), 77 (16), 51 (10). 1H NMR (500.1 MHz,
CDCl3): dH¼3.97 (3H, s, Me), 7.02 (1H, s, C4H), 7.33e7.37 (1H, m, CH
of Ar), 7.40e7.7.42 (1H, m, CH of Ar), 7.44e7.48 (2H, m, 2CH of Ar),
7.60e7.63 (2H, m, 2CH of Ar). 13C NMR (125.7 MHz, CDCl3): dC¼51.7
(OMe), 98.0 (C4H), 124.0 (2CH of Ar), 126.4 (C3), 126.4 (CH of Ar),
128.3 (CH of Ar), 128.7 (2CH of Ar), 131.3 (CH of Ar), 131.6 (CH of Ar),
133.7 (CH of Ar), 134.8 (CipsoeCO2), 136.8 (CipsoeCl), 142.6 (CipsoeN),
144.2 (C5), 159.4 (CO), 161.9 (CO).
(100),111 (47), 91 (15), 77 (47), 51 (10). 1H NMR (500.1 MHz, CDCl3):
3
3
dH¼1.43 (3H, t, JHH¼7.1 Hz, OCH2Me), 4.45 (2H, q, JHH¼7.1 Hz,
OCH2Me), 7.02 (1H, s, C4H), 7.34e7.38 (1H, m, 1H of Ar), 7.41 (1H, t,
3JHH¼7.3 Hz, CH of Ar), 7.47 (2H, t, 3JHH¼7.1 Hz, 2CH of Ar), 7.52 (2H,
d, 3JHH¼7.3 Hz, 2CH of Ar), 7.63 (2H, d, 3JHH¼7.8 Hz, 2CH of Ar), 7.87
3
(1H, d, JHH¼7.8 Hz, 2CH of Ar). 13C NMR (125.7 MHz, CDCl3):
dC¼14.3 (OCH2Me), 61.2 (OCH2Me), 98.4 (C4H), 124.5 (C3), 124.5
(2CH of Ar), 126.9 (CH of Ar), 128.7 (CH of Ar), 129.1 (2CH of Ar),
131.8 (CH of Ar), 132.1 (CH of Ar), 134.2 (CH of Ar), 135.5 (CipsoeCO2),
137.4 (CipsoeCl), 143.5 (CipsoeN), 144.6 (C5), 159.9 (CO), 161.9 (CO).
4.2.7. Ethyl 5-[(4-chlorobenzoyl)oxy]-1-phenyl-1H-pyrazole-3-car-
boxylate (7g). White powder, mp 123e125 ꢁC, 0.29 g, yield: 78%. IR
(KBr) (nmax, cmꢀ1): 1758 (C]O), 1710 (C]O), 1593 and 1437 (Ar),
1230 and 1100 (CeO), 778 (CeCl). Anal. Calcd for C19H15ClN2O4
(370.79): C, 61.55; H, 4.08; N, 7.56%. Found: C, 61.57; H, 4.09; N,
7.57%. MS (EI, 70 eV): m/z (%)¼370 (Mþ, 4), 325 (8), 232 (10), 140
(95), 139 (100), 111 (47), 91 (12), 77 (40). 1H NMR (500.1 MHz,
4.2.3. Methyl 5-[(4-chlorobenzoyl)oxy]-1-phenyl-1H-pyrazole-3-car-
boxylate (7c). White powder, mp 150e152 ꢁC, 0.25 g, yield: 70%. IR
(KBr) (nmax, cmꢀ1): 1739 (C]O), 1688 (C]O), 1591 and 1453 (Ar),
1230 and 1167 (CeO), 768 (CeCl). Anal. Calcd for C18H13ClN2O4
(356.76): C, 60.60; H, 3.67; N, 7.85%. Found: C, 60.71; H, 3.70; N,
7.88%. MS (EI, 70 eV): m/z (%)¼359 (Mþþ2, 7), 357 (Mþ, 19), 325
(Mþꢀ5, 18), 218 (17), 139 (100), 111(30), 77 (38), 51 (11). 1H NMR
(500.1 MHz, CDCl3): dH¼3.98 (3H, s, Me), 7.01 (1H, s, C4H), 7.41 (1H,
3
CDCl3): dH¼1.42 (3H, t, JHH¼7.1 Hz, CH2Me), 4.46 (2H, q,
3JHH¼7.5 Hz, CH2Me), 6.99 (1H, s, C4H), 7.41e7.49 (5H, m, 5CH of Ar),
3
3
7.62 (2H, d, JHH¼8.2 Hz, 2CH of Ar), 7.98 (2H, JHH¼8.4 Hz, 3CH of
Ar). 13C NMR (125.7 MHz, CDCl3): dC¼13.9 (CH2Me), 60.8 (CH2Me),
97.8 (C4H), 123.7 (2CH of Ar), 125.4 (C3), 128.2 (CH of Ar), 128.8 (2CH
of Ar), 128.9 (2CH of Ar), 131.3 (2CH of Ar), 136.9 (CipsoeCO2), 140.9
(CipsoeN), 143.0 (CipsoeCl), 144.2 (C5), 160.2 (CO), 161.5 (CO).
3
t, JHH¼7.5 Hz, CH of Ar), 7.47e7.51 (4H, m, 4CH of Ar), 7.64e7.68
3
(3H, m, 3CH of Ar), 7.98 (2H, d, JHH¼8.5 Hz, 2CH of Ar). 13C NMR
(125.7 MHz, CDCl3): dC¼52.2 (OMe), 98.4 (C4H), 124.2 (2CH of Ar),
125.9 (C3), 128.6 (CipsoeCO2), 128.7 (CH of Ar), 129.2 (2CH of Ar),
129.4 (2CH of Ar), 131.7 (2CH of Ar), 137.3 (CipsoeN), 141.4 (CipsoeCl),
143.1 (C5), 160.6 (CO), 162.3 (CO).
4.2.8. Ethyl 5-[(4-bromobenzoyl)oxy]-1-phenyl-1H-pyrazole-3-car-
boxylate (7h). White powder, mp 129e131 ꢁC, 0.33 g, yield: 80%. IR
(KBr) (nmax, cmꢀ1): 1719 (2C]O),1590 and 1449 (Ar),1264 and 1170
(CeO), 754 (CeBr). Anal. Calcd for C19H15BrN2O4 (415.24): C, 54.96;
H, 3.64; N, 6.75%. Found: C, 54.99; H, 3.63; N, 6.76%. MS (EI, 70 eV):
m/z (%)¼417 (Mþþ2, 10), 415 (Mþ, 10), 371 (13), 369 (13), 187 (98),
185 (100), 157 (31), 105 (7), 91 (6), 77 (36), 51 (5). 1H NMR
4.2.4. Methyl 5-[(4-bromobenzoyl)oxy]-1-phenyl-1H-pyrazole-3-car-
boxylate (7d). White powder, mp 167e169 ꢁC, 0.31 g, yield: 78%. IR
(KBr) (nmax, cmꢀ1): 1736 (C]O), 1652 (C]O), 1588 and 1453 (Ar),
1229 and 1168 (CeO), 772 (CeBr). Anal. Calcd for C18H13BrN2O4
(401.21): C, 53.89; H, 3.27; N, 6.98%. Found: C, 53.72; H, 3.26; N,
6.99%. MS (EI, 70 eV): m/z (%)¼403 (Mþþ2, 2), 401 (Mþ, 2), 218 (10),
185 (100),183 (97),155 (27),105 (7), 91 (11), 77 (47), 51 (13). 1H NMR
(500.1 MHz, CDCl3): dH¼3.98 (3H, s, Me), 7.01 (1H, s, C4H), 7.43 (1H, t,
3JHH¼7.4 Hz, CH of Ar), 7.48 (2H, t, 3JHH¼7.3 Hz, 2CH of Ar), 7.62 (2H,
d, 3JHH¼8.0 Hz, 2CH of Ar), 7.64 (2H, d, 3JHH¼8.5 Hz, 2CH of Ar), 7.90
3
(500.1 MHz, CDCl3): dH¼1.42 (3H, t, JHH¼7.1 Hz, OCH2Me), 4.45
3
(2H, q, JHH¼7.1 Hz, OCH2Me), 7.00 (1H, s, C4H), 7.42 (1H, t,
3JHH¼7.3 Hz, CH of Ar), 7.48 (2H, t, 3JHH¼7.9 Hz, 2CH of Ar), 7.62 (2H,
d, 3JHH¼7.9 Hz, 2CH of Ar), 7.64 (2H, d, 3JHH¼8.6 Hz, 2CH of Ar), 7.90
3
(2H, d, JHH¼8.5 Hz, 2CH of Ar). 13C NMR (125.7 MHz, CDCl3):
3
(2H, d, JHH¼8.5 Hz, 2CH of Ar). 13C NMR (125.7 MHz, CDCl3):
dC¼14.4 (OCH2Me), 61.3 (OCH2Me), 98.3 (C4H), 124.2 (2CH of Ar),
126.4 (CipsoeBr), 128.7 (CH of Ar), 129.2 (2CH of Ar), 130.1 (C3), 131.8
(2CH of Ar), 132.4 (2CH of Ar), 137.3 (CipsoeCO2), 143.5
(CipsoeN),144.6 (C5), 160.8 (CO), 161.9 (CO).
dC¼52.2 (OMe), 98.4 (C4H), 124.2 (2CH of Ar), 128.8 (CH of Ar), 129.0
(CipsoeBr), 129.2 (2CH of Ar), 130.1 (C3), 131.4 (CipsoeCO2), 131.8 (2CH
of Ar), 132.0 (CipsoeN), 143.1 (C5), 160.8 (CO), 162.3 (CO).
4.2.5. Ethyl
(7e). White powder, mp 172e174 ꢁC, 0.26 g, yield: 77%. IR (KBr)
nmax, cmꢀ1): 1715 (C]O), 1605 (C]O), 1550 and 1456 (Ar), 1248
5-(benzoyloxy)-1-phenyl-1H-pyrazole-3-carboxylate
4.2.9. 1-[3-(Methoxycarbonyl)-1-phenyl-1H-pyrazol-5-yl]-4-methyl
(E)-2-butenedioate (9a). White powder, mp 170e172 ꢁC, 0.25 g,
yield: 75%. IR (KBr) (nmax, cmꢀ1): 1767 (C]O), 1726 (2C]O), 1594
(C]C), 1535 and 1449 (Ar), 1230 and 1129 (CeO). Anal. Calcd for
C16H14N2O6 (330.29): C, 58.18; H, 4.27; N, 8.48%. Found: C, 58.23; H,
4.31; N, 8.50%. MS (EI, 70 eV): m/z (%)¼330 (Mþ, 5), 299 (7), 187
(10), 149 (10), 113 (100), 91 (12), 77 (30), 59 (14). 1H NMR
(500.1 MHz, CDCl3): dH¼3.83 (3H, s, Me), 3.95 (3H, s, Me), 6.92 (1H,
(
and 1160 (CeO). Anal. Calcd for C19H16N2O4 (336.34): C, 67.85; H,
4.79; N, 8.33%. Found: C, 67.90; H, 4.82; N, 8.35%. MS (EI, 70 eV): m/z
(%)¼320 (Mþꢀ16, 43), 264 (29), 232 (71), 186 (35), 158 (39), 105
(66), 91 (100), 91 (83), 77 (100), 51 (21). 1H NMR (500.1 MHz,
3
CDCl3): dH¼1.42 (3H, t, JHH¼7.1 Hz, OCH2Me), 4.45 (2H, q,
3JHH¼7.1 Hz, OCH2Me), 7.00 (1H, s, C4H), 7.41 (1H, t, 3JHH¼7.0 Hz, CH
of Ar), 7.48 (2H, t, 3JHH¼8.0 Hz, 2CH of Ar), 7.49 (2H, t, 3JHH¼7.8 Hz,
d, JHH¼15.8 Hz, CH]CHCO2Me), 6.95 (1H, s, C4H), 6.98 (1H, d,
3
3
3JHH¼15.8 Hz, CH]CHCO2Me), 7.43 (1H, t, JHH¼7.4 Hz, CH of Ar),
3
2CH of Ar), 7.64e7.68 (3H, m, 3CH of Ar), 8.06 (2H, d, JHH¼8.1 Hz,
7.49 (2H, t, 3JHH¼7.3 Hz, 2CH of Ar), 7.56 (2H, d, 3JHH¼7.9 Hz, 2CH of
Ar). 13C NMR (125.7 MHz, CDCl3): dC¼52.2 (OMe), 52.6 (OMe), 98.2
(C4H), 124.1 (2CH of Ar), 128.8 (CH of Ar), 129.3 (2CH of Ar), 130.6
(CH]CHCO2Me), 136.8 (CH]CHCO2Me), 137.1 (CipsoeN), 143.0 (C5),
144.2 (C3), 159.5 (CO), 162.2 (CO), 164.4 (CO).
2CH of Ar). 13C NMR (125.7 MHz, CDCl3): dC¼14.4 (OCH2Me), 61.2
(OCH2Me), 98.3 (C4H), 124.2 (2CH of Ar), 127.5 (C3), 128.6 (CH of Ar),
128.9 (2CH of Ar), 129.2 (2CH of Ar), 130.4 (2CH of Ar), 134.5 (CH of
Ar), 137.5 (CipsoeCO2), 143.5 (CipsoeN), 144.9 (C5), 161.5 (CO), 162.0
(CO).
4.2.10. 1-[3-(Ethoxycarbonyl)-1-phenyl-1H-pyrazol-5-yl]-4-ethyl
(E)-2-butenedioate (9b). White powder, mp 154e156 ꢁC, 0.25 g,
yield: 71%. IR (KBr) (nmax, cmꢀ1): 1719 (3C]O), 1599 and 1453 (Ar),
1266 and 1169 (CeO). Anal. Calcd for C18H18N2O6 (358.35): C, 60.33;
H, 5.06; N, 7.82%. Found: C, 60.35; H, 5.04; N, 7.86%. MS (EI, 70 eV):
m/z (%)¼358 (Mþ, 8), 329 (13), 297 (17), 232 (100), 199 (23), 186
(29), 158 (34), 127 (29), 99 (40), 91 (90), 77 (80), 58 (41). 1H NMR
4.2.6. Ethyl 5-[(2-chlorobenzoyl)oxy]-1-phenyl-1H-pyrazole-3-car-
boxylate (7f). White powder, mp 90e92 ꢁC, 0.28 g, yield: 75%. IR
(KBr) (nmax, cmꢀ1): 1766 (C]O), 1725 (C]O), 1531 and 1445 (Ar),
1229 and 1168 (CeO), 769 (CeCl). Anal. Calcd for C19H15ClN2O4
(370.79): C, 61.55; H, 4.08; N, 7.56%. Found: C, 61.59; H, 4.09; N,
7.60%. MS (EI, 70 eV): m/z (%)¼370 (Mþ, 1), 325 (5), 232 (7), 139