J. Zhang et al. / Tetrahedron 69 (2013) 2352e2356
2355
(ESI): calcd for C12H9F3N4O4Na (MþNa)þ 353.0474, found:
5H), 2.77 (s, 3H), 2.60 (s, 3H); 13C NMR:
129.7, 125.3, 27.8, 10.1; GCeMS: m/z¼201, 158, 130, 77.
d
194.4, 137.4, 135.4, 130.1,
353.0460.
3.2.7. Ethyl 1-(3-aminophenyl)-5-(trifluoromethyl)-1H-1,2,3-
3.2.15. Ethyl 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylate
triazole-4-carboxylate (3g). Colorless oil, 1H NMR:
d
7.32 (t,
(3o).5b White solid, mp: 60.4e60.8, 1H NMR:
d 7.54e7.41 (m, 5H),
J¼8.0 Hz, 1H), 6.91e6.77 (m, 3H), 4.51 (q, J¼7.2 Hz, 2H), 3.83 (b, 2H),
4.42 (q, J¼7.1 Hz, 2H), 2.55 (s, 3H), 1.41 (t, J¼7.1 Hz, 3H); 13C NMR:
1.46 (t, J¼7.1 Hz, 3H); 13C NMR:
d
159.2, 147.6, 139.3, 136.3, 130.1,
d 161.7, 138.8, 136.7, 135.4, 130.1, 129.7, 125.3, 61.0, 14.4, 10.0;
129.4 (q, J¼42.0 Hz), 118.8 (q, J¼271.1 Hz), 117.3, 115.2, 111.7, 62.3,
GCeMS: m/z¼231, 158, 130, 77.
14.0; 19F NMR:
d
ꢁ55.8 (s, 3F); HRMS (ESI): calcd for
C12H11F3N4O2Na (MþNa)þ 323.0732, found: 323.0717.
3.2.16. 1-(1-(4-Methoxyphenyl)-5-methyl-1H-1,2,3-triazol-4-yl)
ethanone (3p).4a White solid, mp: 113.4e113.7 ꢀC, 1H NMR:
3.2.8. Ethyl 5-(difluoromethyl)-1-phenyl-1H-1,2,3-triazole-4-
d
7.36e7.04 (m, 4H), 3.88 (s, 3H), 2.74 (s, 3H), 2.55 (s, 3H); 13C NMR:
carboxylate (3h). Colorless oil, 1H NMR:
d
7.57e7.54 (m,5H), 7.51
d
194.4, 160.7, 143.5, 137.6, 128.1, 126.7, 114.8, 55.7, 27.8, 10.1;
(t, J¼52.5 Hz, 1H), 4.49 (q, J¼7.1 Hz, 2H), 1.44 (t, J¼7.1 Hz, 3H); 13C
GCeMS: m/z¼231, 188, 146, 107.
3
2
NMR:
d
160.3, 139.0 (t, JCF¼4.6 Hz), 135.9, 133.5 (t, JCF¼25.4 Hz),
1
130.8, 129.4, 125.5, 106.7 (t, JCF¼238.9 Hz), 62.2, 14.2; 19F NMR:
3.2.17. 1,5-Diphenyl-1H-1,2,3-triazole-4-carbonitrile (3q).5b White
d
ꢁ113.4 (d, J¼52.7 Hz, 2F); HRMS (ESI): calcd for C12H11F2N3O2Na
solid, mp: 160.4e161.2 ꢀC, 1H NMR:
d
7.54e7.44 (m, 6H), 7.37e7.35
(MþNa)þ 290.0717, found: 290.0717.
(m, 4H); 13C NMR:
d 143.1, 135.3, 131.1, 130.3, 129.8, 129.4, 129.0,
125.2, 123.3, 120.6, 112.1; GCeMS: m/z¼246, 218, 190, 77.
3.2.9. Ethyl 5-(difluoromethyl)-1-(4-fluorophenyl)-1H-1,2,3-triazole-
4-carboxylate (3i). Colorless oil,1H NMR:
d
7.60e7.57 (m, 2H), 7.54 (t,
3.2.18. 1-(4-Fluorophenyl)-5-phenyl-1H-1,2,3-triazole-4-carbonitrile
J¼52.5 Hz, 1H), 7.28e7.24 (m, 2H), 4.52 (q, J¼7.1 Hz, 2H), 1.48
(3r). White solid, mp: 162.5e162.9 ꢀC, 1H NMR:
d
7.55e7.45 (m,
0
(t, J¼7.1 Hz, 3H); 13C NMR:
d
163.7 (d, 1 JCF¼252.1 Hz), 160.3, 139.0
3H), 7.38e7.35 (m, 4H), 7.20e7.16 (m, 2H); 13C NMR:
d 163.2 (d,
3
2
40
(t, JCF¼4.7 Hz), 133.7 (t, JCF¼25.2 Hz), 131.9 (d,
J
CF
¼3.2 Hz), 127.7
1JCF¼252.1 Hz),143.2, 131.4 (d, 4JCF¼3.4 Hz),131.3, 129.5, 128.9, 127.2
(d, 3JCF¼9.0 Hz), 123.1, 120.6, 116.9 (d, 2JCF¼23.4 Hz), 112.0; 19F NMR:
0
0
(d, 3 JCF¼9.1 Hz),116.5 (d, 2 JCF¼23.4 Hz),106.7 (t,1JCF¼238.9 Hz), 62.3,
14.2; 19F NMR:
d
ꢁ108.9 (m, 1F), ꢁ113.3 (d, J¼52.6 Hz, 2F); HRMS
d
ꢁ109.0 (m, 1F); HRMS (ESI): calcd for C15H9FN4 (MþH)þ 265.0889,
(ESI): calcd for C12H10F3N3O2Na (MþNa)þ 308.0623, found: 308.0622.
found: 265.0887.
3.2.10. Ethyl 5-(difluoromethyl)-1-(p-tolyl)-1H-1,2,3-triazole-4-
3.2.19. 1-(4-Methoxyphenyl)-5-phenyl-1H-1,2,3-triazole-4-carbon-
carboxylate (3j). White solid, mp: 70.7e71.2 ꢀC, 1H NMR:
d
7.52 (t,
itrile (3s).5b White solid, mp: 144.5e144.9 ꢀC, 1H NMR:
d
7.48e7.34
(m, 5H), 7.25 (d, J¼8.29 Hz, 2H), 6.95 (d, J¼8.30 Hz, 2H), 3.84 (s, 3H);
13C NMR:
160.8, 143.0, 131.0, 129.4, 128.9, 128.1, 126.6, 123.4, 120.2,
J¼52.5 Hz, 1H), 7.47e7.35 (m, 4H), 4.52 (q, J¼7.1 Hz, 2H), 2.47 (s,
3H), 1.48 (t, J¼7.1 Hz, 3H); 13C NMR:
d
160.4, 141.2, 138.9 (t,
d
2
3JCF¼4.6 Hz), 133.5 (t, JCF¼25.2 Hz), 133.4, 129.9, 125.3, 106.7 (t,
114.9, 112.3, 55.7; GCeMS: m/z¼276, 248, 233, 205, 115, 77.
1JCF¼238.8 Hz), 62.2, 21.3, 14.2; 19F NMR:
d
ꢁ113.5 (d, J¼52.6 Hz,
2F); HRMS (ESI): calcd for C13H13F2N3O2Na (MþNa)þ 304.0874,
Acknowledgements
found: 304.0862.
We are grateful for financial supports from the National Natural
Science Foundation of China (Grant No. 21072057, 21272070), the
Key Project in the National Science & Technology Pillar Program of
China in the twelfth five-year plan period (2011BAE06B01-15), the
National Basic Research Program of China (973 Program,
2010CB126101), and the National High Technology Research and
Development Program of China (863 Program, 2011AA10A204).
3.2.11. Ethyl 5-(difluoromethyl)-1-(4-methoxyphenyl)-1H-1,2,3-
triazole-4-carboxylate (3k). White solid, mp: 95.9e96.3 ꢀC, 1H
NMR:
d
7.52 (t, J¼52.5 Hz, 1H), 7.51e7.05 (m, 4H), 4.53 (q, J¼7.1 Hz,
2H), 3.91 (s, 3H), 1.49 (t, J¼7.1 Hz, 3H); 13C NMR:
d 161.2, 160.4, 138.8
3
2
(t, JCF¼4.6 Hz), 133.5 (t, JCF¼25.3 Hz), 128.7, 126.9, 114.4, 106.8 (t,
1JCF¼238.6 Hz), 62.1, 55.6, 14.2; 19F NMR:
d
ꢁ113.6 (d, J¼52.2 Hz,
2F); HRMS (ESI): calcd for C13H13F2N3O3Na (MþNa)þ 320.0823,
found: 320.0810.
Supplementary data
3.2.12. Ethyl 1-(3-aminophenyl)-5-(difluoromethyl)-1H-1,2,3-
triazole-4-carboxylate (3l). White solid, mp: 97.9e98.1 ꢀC, 1H
Supplementary data related to this article can be found at http://
NMR:
d
7.45 (t, J¼52.5 Hz, 1H), 7.30e6.80 (m, 4H), 4.49 (q, J¼7.1 Hz,
2H), 3.93 (b, 2H), 1.45 (t, J¼7.1 Hz, 3H); 13C NMR:
d 160.3, 147.4,
138.8, 136.5, 133.3 (t, 2JCF¼25.9 Hz), 129.9, 117.2, 115.1, 111.7, 106.7 (t,
References and notes
1JCF¼239.0 Hz), 62.2, 14.2; 19F NMR:
d
ꢁ113.7 (d, J¼52.3 Hz, 2F);
HRMS (ESI): calcd for C12H12F2N4O2Na (MþNa)þ 305.0826, found:
1. (a) Hein, J. E.; Fokin, V. V. Chem. Soc. Rev. 2010, 39, 1302e1315; (b) Calderone, V.;
Fiamingo, F. L.; Amato, G.; Giorgi, I.; Livi, O.; Martelli, A.; Martinotti, E. Eur. J.
Med. Chem. 2008, 43, 2618e2626; (c) Kalesh, K. A.; Liu, K.; Yao, S. Q. Org. Biomol.
Chem. 2009, 7, 5129e5136; (d) Genin, M. J.; Allwine, D. A.; Anderson, D. J.;
Barbachyn, M. R.; Emmert, D. E. J. Med. Chem. 2000, 43, 953e970; (e) Bock, V.
D.; Perciaccante, R.; Jansen, T. P.; Hiemstra, H.; Maarseveen, J. H. Org. Lett. 2006,
8, 919e922; (f) Dondoni, A. Chem.dAsian J. 2007, 2, 700e708; (g) Agalave, S. G.;
Maujan, S. R.; Pore, V. S. Chem.dAsian J. 2011, 6, 2696e2718.
305.0821.
3.2.13. Ethyl 5-(difluoromethyl)-1-(thiophen-3-yl)-1H-1,2,3-triazole-
4-carboxylate (3m). White solid, mp: 47.3e47.6 ꢀC, 1H NMR:
d
7.72e7.71 (m, 1H), 7.57 (t, J¼52.4 Hz, 1H), 7.49e7.47 (m, 1H),
7.39e7.38 (m, 1H), 4.49 (q, J¼7.1 Hz, 2H), 1.45 (t, J¼7.2 Hz, 3H); 13C
2. (a) Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem., Int. Ed. 2001, 40,
2004e2021; (b) Bock, V. D.; Hiemstra, H.; Maarseveen, J. H. Eur. J. Org. Chem.
3
2
NMR:
d
160.3, 138.8 (t, JCF¼4.6 Hz), 133.3, 132.9 (t, JCF¼25.3 Hz),
1
ꢀ
126.6, 124.0, 121.5, 106.7 (t, JCF¼238.6 Hz), 62.2, 14.2; 19F NMR:
2006, 51e68; (c) Pachon, L. D.; Maarseveen, J. H.; Rothenberg, G. Adv. Synth.
Catal. 2005, 347, 811e815; (d) Alonso, F.; Moglie, Y.; Radivoy, G.; Yus, M. Eur. J.
Org. Chem. 2010, 1875e1884.
d
ꢁ114.4 (d, J¼52.1 Hz, 2F); HRMS (ESI): calcd for C10H9F2N3O2SNa
(MþNa)þ 296.0281, found: 296.0270.
3. (a) Romeiro, G. A.; Pereira, L. O. R.; Souza, M. C. B. V.; Ferreira, V. F.; Cunha, A. C.
Tetrahedron Lett. 1997, 38, 5103e5106; (b) Campos, V. R.; Abreu, P. A.; Castro, H.
~
C.; Rodrigues, C. R.; Jordao, A. K.; Ferreira, V. F.; Souza, M. C. B. V.; Santos, F. da
3.2.14. 1-(5-Methyl-1-phenyl-1H-1,2,3-triazol-4-yl)ethanone
C.; Moura, L. A.; Domingos, T. S.; Carvalho, C.; Sanchez, E. F.; Fuly, A. L.; Cunha,
A. C. Bioorg. Med. Chem. 2009, 17, 7429e7434; (c) Ackermann, L.; Potukuchi, H.
(3n).5b White solid, mp: 101.5e101.8 ꢀC, 1H NMR:
d
7.60e7.45 (m,