Vol. 00, No. 00, 2019
Jacob et al.
7
1-(2,4-Dichlorophenyl)-3,5-dimethyl-4-phenylselanyl-
1H-pyrazole (4e)
127.8, 129.1, 129.2, 129.6, 131.2, 131.8, 139.7, 144.0,
153.1; MS (relative intensity / %) m/z: 77 (100.0), 118
(59.5), 171 (3.9), 191 (2.3), 282 (83.9), 362 (66.3).
Yield: 0.044 g (44%); orange solid; mp 80-82 °C;
1H NMR (400 MHz, CDCl3) d 2.17 (s, 3H, CH3), 2.31 (s,
3H, CH3), 7.12-7.23 (m, 5H, Ar-H), 7.39 (d, 2H, J 1.2 Hz,
Ar-H), 7.56 (t, 1H, J 1.2 Hz, Ar-H); 13C NMR (100 MHz,
CDCl3) d 11.3, 13.0, 101.7, 125.7, 128.0, 128.1, 129.2,
130.1, 130.4, 132.8, 133.3, 135.9, 136.1, 146.2, 154.0;
MS (relative intensity / %) m/z: 77 (24.7), 118 (4.4), 144
(57.8), 157 (5.7), 239 (5.7), 361 (100.0), 396 (75.4); HRMS
(APCI-QTOF) m/z, calcd. for C17H14Cl2N2Se [M + H]+:
396.9778, found: 396.9767.
4-[(4-Fluorophenyl)selanyl]-3,5-dimethyl-1-phenyl-
1H-pyrazole (4j)
Yield: 0.078 g (90%); orange oil; 1H NMR (400 MHz,
CDCl3) d 2.33 (s, 3H, CH3), 2.38 (s, 3H, CH3), 6.89-6.95
(m, 2H, Ar-H), 7.16-7.21 (m, 2H, Ar-H), 7.36-7.40 (m,
1H, Ar-H), 7.44-7.50 (m, 4H, Ar-H); 13C NMR (100 MHz,
CDCl3) d 12.4, 12.9, 103.1, 116.2 (d, J 21.7 Hz), 124.7,
127.2 (d, J 3.4 Hz), 127.8, 129.1, 130.5 (d, J 7.4 Hz),
139.8, 143.9, 153.0, 161.6 (d, J 243.6 Hz); MS (relative
intensity / %) m/z: 77 (94.1), 118 (55.3), 171 (4.7), 175
(3.6), 266 (100.0), 346 (74.7); HRMS (APCI-QTOF)
m/z, calcd. for C17H15FN2Se [M + H]+: 347.0463, found:
347.0459.
3,5-Dimethyl-4-(phenylselanyl)-1H-pyrazole (4f)41
Yield: 0.047 g (75%); white solid; mp 104-105 °C;
1H NMR (400 MHz, CDCl3) d 2.25 (s, 6H, 2CH3), 7.03-7.12
(m, 5H, Ar-H); 13C NMR (100 MHz, CDCl3) d 11.9,
100.1, 125.6, 128.2, 129.1, 133.1, 149.0; MS (relative
intensity / %) m/z: 77 (16.3), 95 (13.2), 118 (1.6), 157
(10.6), 172 (100.0), 252 (58.9).
4-(Butylselanyl)-3,5-dimethyl-1-phenyl-1H-pyrazole (4k)41
1
Yield: 0.069 g (90%); yellowish oil; H NMR
(400 MHz, CDCl3) d 0.90 (t, 3H, J 7.5 Hz, CH3), 1.41
(sext, 2H, J 7.5 Hz, CH2), 1.58 (quint, 2H, J 7.5 Hz, CH2),
2.39 (s, 3H, CH3), 2.40 (s, 3H, CH3), 2.58 (t, 2H, J 7.5 Hz,
CH2), 7.33-7.37 (m, 1H, Ar-H), 7.41-7.47 (m, 4H, Ar-H);
13C NMR (100 MHz, CDCl3) d 12.5, 13.0, 13.5, 22.7, 28.3,
32.3, 103.2, 124.6, 127.4, 129.0, 140.0, 143.2, 152.8; MS
(relative intensity / %) m/z: 57 (6.1), 77 (72.3), 118 (75.4),
171 (100.0), 251 (24.3), 308 (43.9).
3,5-Dimethyl-1-phenyl-4-(4-tolylselanyl)-1H-pyrazole
(4g)40,41
Yield: 0.066 g (77%); slightly orange solid; mp
96-97 °C; 1H NMR (400 MHz, CDCl3) d 2.27 (s, 3H, Ar-
CH3), 2.33 (s, 3H, CH3), 2.38 (s, 3H, CH3), 7.01-7.03 (m,
2H,Ar-H), 7.10-7.13 (m, 2H,Ar-H), 7.34-7.40 (m, 1H,Ar-
H), 7.44-7.47 (m, 4H,Ar-H); 13C NMR (100 MHz, CDCl3)
d 12.4, 12.9, 20.9, 103.0, 124.7, 127.6, 128.7, 128.97,
129.04, 129.9, 135.6, 139.9, 143.8, 153.1; MS (relative
intensity / %) m/z: 77 (55.1), 118 (32.1), 170 (3.9), 171
(5.7), 262 (100.0), 342 (46.7).
2-[(3,5-Dimethyl-1-phenyl-1H-pyrazol-4-yl)selanyl]pyridine
(4l)
Yield: 0.048 g (58%); colorless oil; 1H NMR (400 MHz,
CDCl3) d 2.35 (s, 3H, CH3), 2.40 (s, 3H, CH3), 6.88 (dt,
1H, J 8.0, 0.9 Hz, Ar-H), 7.02 (ddd, 1H, J 7.4, 4.8, 0.9 Hz,
Ar-H), 7.37-7.44 (m, 2H, Ar-H), 7.48-7.50 (m, 4H,
Ar-H), 8.43 (ddd, 1H, J 4.8, 1.9, 0.9 Hz, Ar-H); 13C NMR
(100 MHz, CDCl3) d 12.4, 12.9, 102.2, 120.0, 121.9,
124.7, 127.8, 129.1, 136.6, 139.8, 144.3, 149.9, 153.2,
158.7; MS (relative intensity / %) m/z: 77 (53.5), 118
(31.9), 156 (11.0), 171 (100.0), 248 (54.9), 329 (31.5);
HRMS (APCI-QTOF) m/z calcd. for C16H15N3Se [M + H]+:
330.0509, found: 330.0520.
4-[(4-Methoxyphenyl)selanyl]-3,5-dimethyl-1-phenyl-
1H-pyrazole (4h)40,41
1
Yield: 0.075 g (84%); red oil; H NMR (400 MHz,
CDCl3) d 2.34 (s, 3H, CH3), 2.39 (s, 3H, CH3), 3.75 (s,
3H, OCH3), 6.76-6.80 (m, 2H, Ar-H), 7.19-7.22 (m, 2H,
Ar-H), 7.34-7.38 (m, 1H, Ar-H), 7.43-7.48 (m, 4H, Ar-H);
13C NMR (100 MHz, CDCl3) d 12.4, 12.9, 55.2, 103.9,
114.9, 122.6, 124.7, 127.6, 129.0, 131.1, 139.9, 143.6,
152.9, 158.5; MS (relative intensity / %) m/z: 77 (39.7),
118 (22.1), 171 (2.0), 187 (1.5), 278 (100.0), 358 (32.2).
General procedure for synthesis of 1,3,5-triphenyl-
4-[(4-Chlorophenyl)selanyl]-3,5-dimethyl-1-phenyl-
1H-pyrazole (4i)40,41
4-(phenylselanyl)-1H-pyrazole (4m)
Yield: 0.073 g (81%); yellowish solid; mp 124-125 °C;
1H NMR (400 MHz, CDCl3) d 2.32 (s, 3H, CH3), 2.37 (s,
3H, CH3), 7.10-7.13 (m, 2H, Ar-H), 7.15-7.18 (m, 2H,
Ar-H), 7.35-7.42 (m, 1H, Ar-H), 7.45-7.50 (m, 4H, Ar-H);
13C NMR (100 MHz, CDCl3) d 12.4, 12.8, 102.3, 124.7,
In a reaction flask of 25.0 mL has added a mixture
of the chalcone 5 (0.25 mmol) and phenylhydrazine
1a (0.25 mmol) in CH3COOH (1.0 mL). The mixture
was stirred for 2 h under reflux, then the temperature
was lowered to 50 °C and the diphenyl diselenide 3a