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Organic & Biomolecular Chemistry
Page 6 of 10
ARTICLE
Journal Name
°C (Lit. mp = 138
̶
140 °C); 1H NMR (400 MHz, CDCl3): δ 7.46−7.42 (m, 1088, 847, 800, 750, 605, 523; HRMS (ESI): calcd for C19H20N3O3S
2H), 7.37 (d, J = 7.6 Hz, 2H), 7.31−7.27 (m, 1H), 7.20 (d, J = 8.0 Hz, 2H), [M+H]+ 370.1220, found 370.1227.
DOI: 10.1039/C7OB02860A
7.02 (d, J = 8.0 Hz, 2H), 3.18 (s, 3H), 2.35 (s, 3H), 2.26 (s, 3H); 13C NMR
2-(4-Chlorophenyl)-1-ethyl-5-methyl-4-(p-tolylthio)-1,2-
(100 MHz, CDCl3): δ 165.3, 159.3, 135.5, 134.8, 133.5, 129.5, 129.1, dihydro-3H-pyrazol-3-one (3g). Colorless solid (261 mg, 73% yield);
127.8, 127.0, 124.6, 99.1, 35.6, 20.8, 11.9; HRMS (ESI): calcd for mp = 143.1 ̶
144.1 °C; 1H NMR (400 MHz, CDCl3): δ 7.42 (d, J = 8.8 Hz,
C18H19N2OS [M+H]+ 311.1213, found 311.1216.
1-Ethyl-5-methyl-2-phenyl-4-(p-tolylthio)-1,2-dihydro-3H-
pyrazol-3-one (3b). Colorless solid (207 mg, 64% yield); mp = 90.4
2H), 7.35 (d, J = 8.8 Hz, 2H), 7.15 (d, J = 8.0 Hz, 2H), 7.02 (d, J = 8.0 Hz,
2H), 3.67 (q, J = 7.2 Hz, 2H), 2.36 (s, 3H), 2.26 (s, 3H), 0.93 (t, J = 7.2
Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 165.9, 159.8, 135.6, 133.5,
̶
91.2 °C; 1H NMR (400 MHz, CDCl3): δ 7.48−7.40 (m, 4H), 7.30 (t, J = 133.2, 132.4, 129.6, 129.3, 127.6, 125.4, 101.6, 43.1, 20.9, 11.9, 10.9;
7.2 Hz, 1H), 7.17 (d, J = 8.4 Hz, 2H), 7.03 (d, J = 8.4 Hz, 2H), 3.70 (q, J IR (neat, cm-1): ν = 2974, 2867, 2826, 1675, 1544, 1489, 1330, 1236,
= 7.0 Hz, 2H), 2.37 (s, 3H), 2.26 (s, 3H), 0.94 (t, J = 7.0 Hz, 3H); 13C 1085, 1011, 805, 604; HRMS (ESI): calcd for C19H20ClN2OS [M+H]+
NMR (100 MHz, CDCl3): δ 165.9, 158.8, 135.4, 134.8, 133.5, 129.6, 359.0979, found 359.0978.
129.2, 127.4, 127.0, 124.6, 100.7, 42.9, 20.8, 11.8, 11.2; IR (neat, cm-
1): ν = 3042. 2977, 2919, 1888, 1661, 1594, 1491, 1345, 1232, 1015, dihydro-3H-pyrazol-3-one (3h). Colorless solid (218 mg, 61% yield);
803, 754, 698, 603; HRMS (ESI): calcd for C19H21N2OS [M+H]+ mp = 140.2 140.8 °C; 1H NMR (400 MHz, CDCl3): δ 7.53−7.51 (m, 1H),
2-(2-Chlorophenyl)-1-ethyl-5-methyl-4-(p-tolylthio)-1,2-
̶
325.1375, found 325.1381.
5-Methyl-1-pentyl-2-phenyl-4-(p-tolylthio)-1,2-dihydro-3H-
pyrazol-3-one (3c). Colorless solid (264 mg, 72% yield); mp = 83.2
7.42−7.36 (m, 3H), 7.17 (d, J = 8.4 Hz, 2H), 7.03 (d, J = 8.4 Hz, 2H),
3.66−3.56 (m, 1H), 3.54−3.44 (m, 1H), 2.34 (s, 3H), 2.26 (s, 3H), 1.07
(t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 165.9, 156.9, 135.0,
̶
84.4 °C; 1H NMR (400 MHz, CDCl3): δ 7.48−7.43 (m, 2H), 7.38 (d, J = 134.1, 133.6, 132.5, 130.8, 130.7, 130.5, 129.5, 127.7, 126.9, 97.8,
7.2 Hz, 2H), 7.30 (t, J = 7.2 Hz, 1H), 7.16 (d, J = 8.4 Hz, 2H), 7.02 (d, J 42.2, 20.8, 12.4, 11.5; IR (neat, cm-1): ν = 3026, 2959, 2918, 1650,
= 8.0 Hz, 2H), 3.63 (t, J = 7.2 Hz, 2H), 2.36 (s, 3H), 2.26 (s, 3H), 1536, 1475, 1415, 1341, 1238, 1082, 800, 750, 602; HRMS (ESI): calcd
1.39−1.31 (m, 2H), 1.21−1.13 (m, 2H), 1.11−1.04 (m, 2H), 0.80 (t, J = for C19H20ClN2OS [M+H]+ 359.0979, found 359.0985.
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 165.9, 158.5, 135.2, 134.8,
133.7, 129.5, 129.1, 127.2, 127.1, 124.8, 98.9, 47.7, 28.3, 26.6, 22.0, dihydro-3H-pyrazol-3-one (3i). Off-white solid (192 mg, 55% yield);
20.8, 13.6, 11.9; IR (neat, cm-1): ν = 2917, 2855, 1672, 1595, 1533, mp = 126.5 127.2 °C; 1H NMR (400 MHz, CDCl3): δ 7.21−7.15 (m, 4H),
2-(3,4-Dimethylphenyl)-1-ethyl-5-methyl-4-(p-tolylthio)-1,2-
̶
1489, 1247, 1083, 802, 752, 690, 651, 604; HRMS (ESI): calcd for 7.09 (dd, J = 8.0, 1.8 Hz, 1H), 7.02 (d, J = 8.0 Hz, 2H), 3.67 (q, J = 7.2
C22H27N2OS [M+H]+ 367.1839, found 367.1845.
Hz, 2H), 2.34 (s, 3H), 2.28 (s, 3H), 2.27 (s, 3H), 2.26 (s, 3H), 0.94 (t, J =
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 166.0, 157.9, 137.7, 136.0,
1-Benzyl-5-methyl-2-phenyl-4-(p-tolylthio)-1,2-dihydro-3H-
pyrazol-3-one (3d).16 Pale yellow solid (161 mg, 42% yield); mp = 135.2, 133.8, 132.4, 130.2, 129.5, 127.3, 126.2, 122.4, 100.2, 42.7,
117.1 ̶
118.7 °C; 1H NMR (400 MHz, CDCl3): δ 7.47−7.43 (m, 2H), 7.38 20.9, 19.8, 19.4, 11.7, 11.4; IR (neat, cm-1): ν = 2974, 2919, 2854,
(d, J = 7.2 Hz, 2H), 7.33−7.24 (m, 4H), 7.00−6.92 (m, 6H), 4.79 (s, 2H), 1876, 1667, 1495, 1409, 1330, 1099, 815, 794, 737, 596; HRMS (ESI):
2.38 (s, 3H), 2.25 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 165.5, 159.3, calcd for C21H25N2OS [M+H]+ 353.1682, found 353.1690.
135.1, 134.7, 133.8, 133.3, 129.5, 129.2, 128.7, 128.4, 127.2, 127.1,
126.8, 124.8, 100.9, 51.2, 20.8, 12.3; HRMS (ESI): calcd for (3j). Colorless solid (168 mg ,68% yield); mp = 152.3 ̶ 153.1 °C; H
C24H23N2OS [M+H]+ 387.1526, found 387.1535.
1,2,5-Trimethyl-4-(p-tolylthio)-1,2-dihydro-3H-pyrazol-3-one
1
NMR (400 MHz, CDCl3): δ 7.09 (d, J = 8.0 Hz, 2H), 6.99 (d, J = 8.0 Hz,
2H), 3.40 (s, 3H), 3.38 (s, 3H), 2.24 (s, 6H); 13C NMR (100 MHz, CDCl3):
1-Ethyl-2-(4-methoxyphenyl)-5-methyl-4-(p-tolylthio)-1,2-
dihydro-3H-pyrazol-3-one (3e). Pale yellow solid (244 mg, 69% δ 165.5, 154.1, 135.1, 134.3, 129.5, 127.0, 96.2, 33.4, 29.4, 20.9, 11.3;
yield); mp = 150.8
151.6 °C; 1H NMR (400 MHz, CDCl3): δ 7.30 (d, J = IR (neat, cm-1): ν = 3052, 2918, 2850, 1630, 1519, 1402, 1361, 1226,
̶
8.8 Hz, 2H), 7.16 (d, J = 8.0 Hz, 2H), 7.02 (d, J = 8.0 Hz, 2H), 6.97 (d, J 1031, 1011, 810, 741, 569, 514; HRMS (ESI) calcd for C13H17N2OS
= 8.8 Hz, 2H), 3.82 (s, 3H), 3.65 (q, J = 7.2 Hz, 2H), 2.34 (s, 3H), 2.26 [M+H]+ 249.1056, found 249.1060.
(s, 3H), 0.95 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 166.1,
158.8, 157.6, 135.3, 133.8, 129.5, 127.3, 126.9, 124.6, 114.6, 99.9, one (3k). Colorless solid (149 mg, 57% yield); mp = 69.3
1-Ethyl-2,5-dimethyl-4-(p-tolylthio)-1,2-dihydro-3H-pyrazol-3-
70.3 °C; 1H
̶
55.5, 42.5, 20.9. 11.7, 11.5; IR (neat, cm-1): ν = 2955, 2924, 2854, NMR (400 MHz, CDCl3): δ 7.05 (d, J = 8.0 Hz, 2H), 6.99 (d, J = 8.0 Hz,
1676, 1552, 1508, 1250, 1115, 1096, 1017, 834, 804, 585; HRMS (ESI): 2H), 3.81 (q, J = 7.2 Hz, 2H), 3.38 (s, 3H), 2.24 (s, 3H), 2.23 (s, 3H), 1.10
calcd for C20H23N2O2S [M+H]+ 355.1475, found 355.1478.
(t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 166.0, 154.0, 135.0,
134.1, 129.4, 126.6, 97.4, 41.4, 29.3, 20.8, 12.7, 10.9; IR (neat, cm-1):
1-Ethyl-5-methyl-2-(4-nitrophenyl)-4-(p-tolylthio)-1,2-dihydro-
3H-pyrazol-3-one (3f). Pale yellow solid (65 mg, 18% yield); mp = ν = 2973, 2921, 1624, 1490, 1416, 1254, 1210, 1071, 803, 749, 603;
152.6
153.2 °C; 1H NMR (400 MHz, CDCl3): δ 8.32 (d, J = 9.2 Hz, 2H), HRMS (ESI): calcd for C14H18N2OSNa [M+Na]+ 285.1032, found
7.63 (d, J = 9.2 Hz, 2H), 7.17 (d, J = 8.0 Hz, 2H), 7.04 (d, J = 8.0 Hz, 2H), 285.1037.
̶
3.74 (q, J = 7.2 Hz, 2H), 2.41 (s, 3H), 2.27 (s, 3H), 0.94 (t, J = 7.2 Hz,
1-Ethyl-2-phenyl-5-propyl-4-(p-tolylthio)-1,2-dihydro-3H-
3H); 13C NMR (100 MHz, CDCl3): δ 165.8, 162.4, 145.1, 140.6, 136.1, pyrazol-3-one (3l). Colorless solid (172 mg, 49% yileld); mp = 123.3
̶
132.3, 129.7, 128.0, 124.8, 122.7, 103.5, 43.9, 20.9, 12.2, 10.4; IR 124.5 °C; 1H NMR (400 MHz, CDCl3): δ 7.48−7.40 (m, 4H), 7.32−7.28
(neat, cm-1): ν = 2962, 2920, 2852, 1682, 1590, 1519, 1492, 1329, (m, 1H), 7.17 (d, J = 8.0 Hz, 2H), 7.02 (d, J = 8.0 Hz, 2H), 3.69 (q, J =
6.8 Hz, 2H), 2.73 (t, J = 7.6 Hz, 2H), 2.26 (s, 3H), 1.72−1.62 (m, 2H),
6 | J. Name., 2012, 00, 1-3
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