10.1002/ejoc.201901886
European Journal of Organic Chemistry
FULL PAPER
1.30 Hz, 2H, ArH), 8.16 (d, J = 2.76 Hz, 1H, C=CH); 13C NMR (150 MHz,
CDCl3): δ = 106.5, 115.7 (J = 21.51 Hz), 115.7 (J = 21.51 Hz), 127.6 (J =
3.18 Hz), 128.1, 128.1, 128.3 (J = 8.30 Hz), 128.3 (J = 8.30 Hz), 129.4,
129.4, 132.8, 134.5, 137.1, 156.1, 163.4 (J = 249.10 Hz); 19F NMR (565
3-([1,1'-Biphenyl]-4-yl)-1-(phenylsulfonyl)-1H-pyrazole (3k)
:
solid; mp 155–157 C; IR (KBr): 1654, 1450, 1379, 1322, 1184, 1153,
1123, 1038, 761, 729, 687,618, 594; 1H NMR (600 MHz, CDCl3): δ =
6.78 (d, J = 2.82 Hz, 1H, C=CH), 7.37–7.40 (m, 1H, ArH), 7.46–7.49 (m,
2H, ArH), 7.56–7.58 (m, 2H, ArH), 7.62–7.68 (m, 5H, ArH), 7.92 (d, J =
8.40 Hz, 2H, ArH), 8.10 (d, J = 8.52 Hz, 2H, ArH), 8.18 (d, J = 2.76 Hz,
1H, C=CH); 13C NMR (150 MHz, CDCl3): δ = 106.7, 126.9, 126.9, 127.0,
127.0, 127.4, 127.4, 127.6, 128.1, 128.1, 128.9, 128.9, 129.4, 129.4,
130.3, 132.7, 134.5, 137.2, 140.4, 142.0, 156.8; HRMS (TOF ES+): m/z
calcd for C21H17N2O2S+ [M+H]+, 361.1005; found, 361.1005.
White
MHz, CDCl3):
δ =
-111.9; HRMS (TOF ES+): m/z calcd for
C15H12FN2O2S+ [M+H]+, 303.0598; found, 303.0598.
3-(2-Chlorophenyl)-1-(phenylsulfonyl)-1H-pyrazole (3f): Yellow solid;
mp 147–149 C; IR (KBr): 1631, 1448, 1384, 1318, 1189, 1150, 1052,
756, 728, 610, 594; 1H NMR (600 MHz, CDCl3): δ = 6.95 (d, J = 2.82 Hz,
1H, C=CH), 7.32–7.33 (m, 2H, ArH), 7.43–7.45 (m, 1H, ArH), 7.57–7.59
(m, 2H, ArH), 7.67–7.69 (m, 1H, ArH), 7.77–7.78 (m, 1H, ArH), 8.09 (d, J
= 8.58 Hz, 2H, ArH), 8.18 (d, J = 2.82Hz, 1H, C=CH); 13C NMR (150 MHz,
CDCl3): δ = 110.4, 126.9, 128.2, 128.2, 129.4, 129.4, 130.1, 130.3, 130.5,
131.1, 131.6, 132.6, 134.6, 137.1, 155.1; HRMS (TOF ES+): m/z calcd for
C15H12ClN2O2S+ [M+H]+, 319.0303; found, 319.0304.
(E)-1-(Phenylsulfonyl)-3-styryl-1H-pyrazole (3l): White solid; mp 120–
122 C; IR (KBr): 1631, 1525, 1420, 1316, 1186, 1175, 1140, 1044, 768,
726, 614, 577; 1H NMR (600 MHz, CDCl3): δ = 6.65 (d, J = 3.36 Hz, 1H,
C=CH), 7.13 (d, J = 4.80 Hz, 3H, ArH),7.38–7.38 (m, 2H, C=CH), 7.48–
7.49 (m, 3H, ArH), 7.55–7.58 (m, 2H, ArH), 8.05 (d, J = 8.22 Hz, 2H, ArH),
8.09 (d, J = 3.36 Hz, 1H, C=CH); 13C NMR (150 MHz, CDCl3): δ = 106.4,
119.2, 126.8, 126.8, 128.0, 128.0, 128.6, 128.8, 128.8, 129.4, 129.4,
132.4, 134.1, 134.5, 136.1, 137.2, 156.5; HRMS (TOF ES+): m/z calcd for
C17H15N2O2S+ [M+H]+, 311.0849; found, 311.0849.
3-(4-Nitrophenyl)-1-(phenylsulfonyl)-1H-pyrazole (3g): Yellow liquid;
IR (KBr): 1604, 1516, 1392, 1351, 1317, 1189, 1150, 1107, 1042, 854,
775, 610, 594; 1H NMR (600 MHz, CDCl3): δ = 6.82 (d, J = 2.82 Hz, 1H,
C=CH), 7.59–7.62 (m, 2H, ArH), 7.69–7.72 (m, 1H, ArH), 8.00 (d, J =
8.76 Hz, 2H, ArH), 8.11 (d, J = 8.55 Hz, 2H, ArH), 8.23 (d, J = 2.82 Hz,
1H, C=CH), 8.28 (d, J = 8.76 Hz, 2H, ArH); 13C NMR (150 MHz, CDCl3):
δ = 106.9, 124.1, 124.1, 127.1, 127.1, 127.1, 127.1, 128.3, 128.3, 129.5,
129.5, 133.0, 134.9, 136.8, 137.5, 148.1, 154.6; HRMS (TOF ES+): m/z
calcd for C15H12N3O4S+ [M+H]+, 330.0543; found, 330.0545.
1-(Phenylsulfonyl)-3-(thiophen-2-yl)-1H-pyrazole (3m): Yellow solid;
mp 97–99 C; IR (KBr): 1559, 1449, 13931317, 1187, 1144, 1043, 779,
728, 612, 588; 1H NMR (600 MHz, CDCl3): δ = 6.52 (d, J = 2.88 Hz, 1H,
C=CH), 6.97 (d, J = 5.07 Hz, 1H, C=CH2), 7.24 (d, J = 5.04 Hz, 1H,
C=CH2), 7.33 (d, J = 3.6 Hz, 1H, C=CH2), 7.45–7.47 (m, 2H, ArH), 7.54–
7.57 (m, 1H, ArH), 7.97 (d, J = 8.58 Hz, 2H, ArH), 8.02 (d, J = 2.82 Hz,
1H, C=CH); 13C NMR (150 MHz, CDCl3): δ = 105.8, 125.1, 125.6, 126.5,
127.1, 127.1, 128.3, 128.3, 131.6, 133.4, 133.4, 136.3, 151.2; HRMS
1-(Phenylsulfonyl)-3-(4-(trifluoromethyl)phenyl)-1H-pyrazole
(3h):
Yellow solid; mp 112–114 C; IR (KBr): 1617, 1560, 1383, 1324, 1191,
1128, 1063, 1035, 776, 729, 619, 591; 1H NMR (600 MHz, CDCl3): δ =
6.78 (d, J = 2.76 Hz, 1H, C=CH), 7.57–7.60 (m, 2H, ArH), 7.67–7.70 (m,
3H, ArH), 7.95 (d, J = 8.04 Hz, 2H, ArH), 8.10 (d, J = 8.61 Hz, 2H, ArH),
8.20 (d, J = 2.76 Hz, 1H, C=CH); 13C NMR (150 MHz, CDCl3): δ = 106.7,
106.7, 124.0 (d, J = 272.3 Hz), 125.7 (q, J = 7.6 Hz), 126.7, 126.7, 128.2,
128.2, 129.5, 129.5, 131.0 (d, J = 32.6 Hz), 132.9, 134.7, 134.8, 137.0,
155.5; 19F NMR (565 MHz, CDCl3): δ = -62.7; HRMS (TOF ES+): m/z
calcd for C16H12F3N2O2S+ [M+H]+, 353.0566; found, 353.0566.
+
(TOF ES+): m/z calcd for C13H11N2O2S2 [M+H]+, 291.0256; found,
291.0257.
3-(adamantan-1-yl)-1-(phenylsulfonyl)-1H-pyrazole (3n): White solid;
mp 113–115 C; IR (KBr): 2911, 2852, 1686, 1532, 1449, 1383, 1289,
1188, 1138, 1031, 773, 726, 687, 616, 591; 1H NMR (600 MHz, CDCl3): δ
=1.73 (q, J = 12.2 Hz, 6H, 3CH2), 1.86 (d, J = 2.4 Hz, 6H, 3CH2), 2.02 (s,
3H, 3CH), 6.27 (d, J = 2.8 Hz, 1H, C=CH), 7.51 (m, 2H, ArH), 7.61 (m,
1H, ArH), 7.97–7.95 (m, 2H, ArH), 7.98 (d, J = 0.6 Hz, 1H, C=CH); 13C
NMR (150 MHz, CDCl3): δ = 28.4, 28.4, 28.4, 34.5, 36.6, 36.6, 36.6, 41.8,
41.8, 41.8, 106.2, 127.8, 127.8, 129.1, 129.1, 131.9, 134.1, 137.6, 168.3;
HRMS (TOF ES+): m/z calcd for C19H23N2O2S+ [M+H]+, 343.1475; found,
343.1458.
3-(4-(Methylsulfonyl)phenyl)-1-(phenylsulfonyl)-1H-pyrazole
(3i):
White solid; mp 164–166 C; IR (KBr): 1631, 1529, 1450, 1305, 1186,
1148, 1092, 1041, 759, 729, 609, 596; 1H NMR (600 MHz, CDCl3): δ =
3.08 (s, 3H, SO2CH3), 6.81 (d, J = 2.82 Hz, 1H, C=CH), 7.58–7.60 (m, 2H,
ArH), 7.68–7.71 (m, 1H, ArH), 7.98–8.04 (m, 4H, ArH), 8.10 (d, J = 8.13
Hz, 2H, ArH), 8.22 (d, J = 2.88 Hz, 1H, C=CH); 13C NMR (150 MHz,
CDCl3): δ = 44.5, 106.8, 127.2, 127.2, 127.9, 127.9, 128.2, 128.2, 129.5,
129.5, 133.0, 134.8, 136.7, 136.8, 140.7, 154.9; HRMS (TOF ES+): m/z
calcd for C16H15N2O4S2+ [M+H]+, 363.0468; found, 363.0468.
3-Phenyl-1-tosyl-1H-pyrazole (3o): White solid; mp 139–141 C; IR
(KBr): 1592, 1502, 1389, 1323, 1190, 1170, 1156, 1033, 813, 763, 688,
585; 1H NMR (600 MHz, CDCl3): δ = 2.43 (s, 3H, ArCH3), 6.72 (d, J =
2.76 Hz, 1H, C=CH), 7.34 (d, J = 8.16 Hz, 2H, ArH), 7.37–7.43 (m, 3H,
ArH), 7.82–7.84 (m, 2H, ArH), 7.96 (d, J = 8.52 Hz, 2H, ArH), 8.15 (d, J =
2.82 Hz, 1H, C=CH); 13C NMR (150 MHz, CDCl3): δ = 21.7, 126.4, 126.4,
128.2, 128.2, 128.7, 128.7, 129.2, 130.0, 130.0, 131.5, 132.5, 134.2,
145.7, 156.9; HRMS (TOF ES+): m/z calcd for C16H15N2O2S+ [M+H]+,
299.0849; found, 299.0850.
2-(1-(Phenylsulfonyl)-1H-pyrazol-3-yl)phenol (3j): White solid; mp
137–139 C; IR (KBr): 3240, 1622, 1585, 1531, 1440, 1325, 1186, 1149,
1067, 1041, 749, 726, 683, 606, 586; 1H NMR (600 MHz, CDCl3): δ =
6.82 (d, J = 2.88 Hz, 1H, C=CH), 6.92–6.95 (m, 1H, ArH), 7.04 (d, J =
8.28 Hz, 1H, ArH), 7.28–7.30 (m, 1H, ArH), 7.53 (d, J = 7.8 Hz, 1H, ArH),
7.57–7.60 (m, 2H, ArH), 7.67–7.70 (m, 1H, ArH), 8.06 (d, J = 8.55 Hz, 2H,
ArH), 8.19 (d, J = 2.94 Hz, 1H, C=CH), 10.08 (s, 1H, ArOH); 13C NMR
(150 MHz, CDCl3): δ = 106.2, 114.8, 117.5, 119.6, 127.2, 128.1, 128.1,
129.6, 129.6, 131.1, 131.1, 132.1, 132.1, 134.9, 136.5, 156.3, 157.0;
HRMS (TOF ES+): m/z calcd for C15H13N2O3S+ [M+H]+, 301.0641; found,
301.0643.
3-(4-Methoxyphenyl)-1-tosyl-1H-pyrazole (3p): Yellow solid; mp 91–93
C; IR (KBr): 1612, 1510, 1432, 1378, 1323, 1251, 1175, 1153, 1034,
823, 768, 676, 619, 585; 1H NMR (600 MHz, CDCl3): δ = 2.41 (s, 3H,
ArCH3), 3.83 (s, 3H, ArOCH3), 6.64 (d, J = 2.82 Hz, 1H, C=CH), 6.92 (d,
J = 8.82 Hz, 2H, ArH), 7.32 (d, J = 8.16 Hz, 2H, ArH), 7.75 (d, J = 8.82
Hz, 2H, ArH), 7.93 (d, J = 8.52 Hz, 2H, ArH), 8.10 (d, J = 2.82 Hz, 1H,
C=CH); 13C NMR (150 MHz, CDCl3): δ = 21.7, 55.3, 106.3, 114.0, 114.0,
This article is protected by copyright. All rights reserved.