H
Synthesis
L. A. Souza et al.
Paper
13
1
C NMR (100 MHz, DMSO-d ): δ = 161.2, 156.1, 155.9, 143.6, 135.3,
H NMR (400 MHz, DMSO-d ): δ = 7.83 (s, 1 H), 2.59 (s, 3 H), 1.99 (s,
6
6
131.8, 129.0, 127.9, 104.9, 87.8.
3 H).
+
+
13
GC-MS (EI, 70 eV): m/z (%) = 316 (5) [M + 4] , 314 (30) [M + 2] , 312
(
C NMR (100 MHz, DMSO-d ): δ = 163.3, 156.1, 151.0, 135.5, 107.6,
6
+
30) [M] , 217 (70), 215 (100), 181 (5), 124 (9).
87.7, 13.3, 12.3.
+
+
Anal. Calcd for C12H Cl N : C, 45.96; H, 2.25; N, 17.87. Found: C,
GC-MS (EI, 70 eV): m/z (%) = 300 (8) [M + 4] , 298 (36) [M + 2] , 296
7
3
4
+
45.61; H, 2.58; N, 17.48.
(38) [M] , 263 (80), 261 (90), 229 (30), 227 (95), 207 (100).
Anal. Calcd for C H Cl N S: C, 32.29; H, 2.37; N, 18.81. Found: C,
32.49; H, 2.51; N, 18.42.
8
7
3
4
5-(4-Methoxyphenyl)-7-(trichloromethyl)-[1,2,4]triazolo[1,5-
a]pyrimidine (3e)
Yellow solid; yield: 292 mg (85%), mp 182–183 °C.
2-(Methylthio)-5-phenyl-7-(trichloromethyl)-[1,2,4]triazolo[1,5-
1
a]pyrimidine (3i)
H NMR (400 MHz, DMSO-d ): δ = 8.88 (s, 1 H), 8.36 (d, J = 8.80 Hz,
6
2
H), 8.32 (s, 1 H), 7.19 (d, J = 8.80 Hz, 2 H), 3.92 (s, 3 H).
Yellow solid; yield: 259 mg (72%); mp 137–139 °C.
13
1
C NMR (100 MHz, DMSO-d ): δ = 162.4, 160.7, 156.2, 155.7, 143.5,
H NMR (400 MHz, DMSO-d ): δ = 8.29–8.27 (m, 2 H), 8.24 (s, 1 H),
6
6
129.8, 127.6, 114.5, 104.3, 87.8, 55.4.
7.60–7.58 (m, 3 H), 2.72 (s, 3 H).
+
13
GC-MS (EI, 70 eV): m/z (%) = 308 (75) [M – Cl] , 306 (35), 274 (100),
C NMR (100 MHz, DMSO-d ): δ = 168.2, 160.5, 156.6, 142.4, 135.3,
6
240 (60), 207 (80).
131.8, 129.0, 127.8, 103.8, 87.7, 13.4.
+
Anal. Calcd for C13H Cl N O: C, 45.44; H, 2.64; N, 16.31. Found: C,
GC-MS (EI, 70 eV): m/z (%) = 324 (20) [M – Cl] , 292 (35), 290 (100),
9
3
4
45.28; H, 2.87; N, 16.34.
255 (90), 245 (75), 211 (50), 128 (35), 77 (35).
Anal. Calcd for C13H Cl N S: C, 43.41; H, 2.52; N, 15.58. Found: C,
43.79; H, 2.81; N, 15.37.
9
3
4
2-(Methylthio)-7-(trichloromethyl)-[1,2,4]triazolo[1,5-a]pyrimi-
dine (3f) and 2-(Methylthio)-5-(trichloromethyl)-[1,2,4]triazo-
lo[1,5-a]pyrimidine (3f′)
5-(4-Methoxyphenyl)-2-(methylthio)-7-(trichloromethyl)-
Yellow solid; yield: 190 mg (67%); isomers obtained in the proportion
[1,2,4]triazolo[1,5-a]pyrimidine (3j)
of 60% (3f) and 10% (3f′)
Beige solid; yield: 327 mg (84%); mp 173–174 °C.
1
H NMR (400 MHz, DMSO-d ): δ = 8.29 (d, J = 8.78 Hz, 2 H), 8.19 (s,
6
Data for 3f
1
13
H), 7.14 (d, J = 8.77 Hz, 2 H), 3.87 (s, 3 H), 2.71 (s, 3 H).
1
H NMR (400 MHz, DMSO-d ): δ = 9.04 (d, J = 4.85 Hz, 1 H), 7.95 (d,
6
C NMR (100 MHz, DMSO-d ): δ = 167.8, 162.4, 160.2, 156.7, 142.3,
6
J = 4.84 Hz, 1 H), 2.70 (s, 3 H).
129.7, 127.6, 114.5, 103.1, 87.8, 55.4, 13.4.
13
C NMR (100 MHz, DMSO-d ): δ = 167.8, 156.6, 155.3, 142.1, 106.9,
6
+
GC-MS (EI, 70 eV): m/z (%) = 272 (100) [M – CCl ] , 227 (35), 185 (25).
3
87.4, 13.4.
Anal. Calcd for C14H11Cl N OS: C, 43.15; H, 2.85; N, 14.38. Found: C,
+
+
3
4
GC-MS (EI, 70 eV): m/z (%) = 286 (10) [M + 4] , 284 (50) [M + 2] , 282
43.18; H, 2.98; N, 14.34.
+
(
50) [M] , 246 (100), 238 (30), 213 (70), 203 (65), 177 (30).
5
-(4-Fluorophenyl)-2-(methylthio)-7-(trichloromethyl)-
Data for 3f′
[
1,2,4]triazolo[1,5-a]pyrimidine (3k)
1
H NMR (400 MHz, DMSO-d ): δ = 9.50 (d, J = 7.16 Hz, 1 H), 7.88 (d,
6
Yellow solid; yield: 257 mg (68%); mp 153–155 °C.
J = 7.32 Hz, 1 H), 2.68 (s, 3 H).
1
H NMR (400 MHz, DMSO-d ): δ = 8.42–8.83 (m, 2 H), 8.27 (s, 1 H),
13
6
C NMR (100 MHz, DMSO-d ): δ = 170.0, 160.2, 153.3, 138.3, 105.8,
6
7
.47–7.42 (m, 2 H), 2.74 (s, 3 H).
87.4, 13.4.
13
C NMR (100 MHz, DMSO-d ): δ = 168.2, 164.4 (d, 1JC–F = 250.9 Hz),
6
3
2
159.5, 156.6, 142.5, 131.8, 130.4 (d, J = 9.0 Hz), 116.1 (d, J = 21.9
C–F C–F
5-Methyl-2-(methylthio)-7-(trichloromethyl)-[1,2,4]triazolo[1,5-
Hz), 103.7, 87.7, 13.4.
a]pyrimidine (3g)
+
+
GC-MS (EI, 70 eV): m/z (%) = 380 (10) [M + 4] , 378 (40) [M + 2] , 376
Yellow solid; yield: 244 mg (82%); mp 115–117 °C.
+
(42) [M] , 344 (85), 342 (100), 307 (80), 297 (70), 271 (80).
1
H NMR (400 MHz, DMSO-d ): δ = 7.84 (s, 1 H), 2.72 (s, 3 H), 2.67 (s,
6
Anal. Calcd for C13H Cl FN S: C, 41.34; H, 2.14; N, 14.84. Found: C,
3
H).
8
3
4
41.04; H, 2.26; N, 14.53.
13
C NMR (100 MHz, DMSO-d ): δ = 167.1, 165.9, 156.3, 141.4, 107.4,
6
8
7.6, 24.9, 13.3.
[
1,2,4]Triazolo[1,5-a]pyrimidinones; General Procedure
+
+
GC-MS (EI, 70 eV): m/z (%) = 300 (<1) [M+4] , 298 (7) [M+2] , 296 (8)
To a stirred solution of starting enone 1 (1 mmol) in MeCN (10 mL)
were added 3-amino-1H-1,2,4-triazole 2 (1 mmol) and Et N (1 mmol)
and the mixture was heated to reflux for 24 h. The solvent was re-
moved under vacuum and the residue was dissolved in EtOAc (20 mL),
then washed twice with acidified H2O (2% HCl), (10 mL). The organic
layer was dried over anhydrous Na SO , filtered and concentrated un-
+
[
M] , 285 (43), 271 (100), 147 (36), 105 (47).
3
Anal. Calcd for C H Cl N S: C, 32.29; H, 2.37; N, 18.83. Found: C,
8
7
3
4
32.21; H, 2.11; N, 18.45.
6
-Methyl-2-(methylthio)-7-(trichloromethyl)-[1,2,4]triazolo[1,5-
2
4
a]pyrimidine (3h)
der vacuum. The final pure product was obtained by recrystallization
from EtOH.
Brown solid; yield: 149 mg (50%); mp 192–194 °C.
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–J