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165.88 (C-5) ppm; IR (KBr): ꢂꢀ¼ 3119 (N-H), 1462, 1548, 1608 (aromatic skeleton), 1249 (C¼S),
1391 (CH3) cmꢁ1; FAB-MS (8kV): m=z ¼ 259 (Mþ 1).
N,N0-Bis(3-ethyl-5-mercapto-1,2,4-triazol-4-yl)hydrazine (3b, C8H14N8S2)
Colorless needles; yield 70%; mp 254–256ꢃC; 1H NMR: ꢁ ¼ 1.14–1.70 (t, 3Hꢄ2, CH3ꢄ2, J ¼ 7.7 Hz),
2.51–2.55 (q, 2Hꢄ2, CH2, J ¼ 7.7 Hz), 13.10 (br, s, 1Hꢄ2, NHꢄ2, NH-1 or NH-6), 13.19 (br, s, 1Hꢄ2,
NHꢄ2, NH-6 or NH-1) ppm; 13C NMR: ꢁ ¼ 10.12 (CH3), 15.74 (CH2), 148.87 (C-3), 165.88 (C-5)
ppm; IR (KBr): ꢂꢀ¼ 3125 (N-H), 1464, 1552, 1602 (aromatic skeleton), 1248 (C¼S), 1389 (CH3)
cmꢁ1; FAB-MS (8kV): m=z ¼ 287 (Mþ 1).
N,N0-Bis(5-mercapto-3-phenyl-1,2,4-triazol-4-yl)hydrazine (3c, C16H14N8S2)
1
Colorless needles; yield: 59%; mp 259–260ꢃC; H NMR: ꢁ ¼ 7.51–7.53, 7.90–7.92 (mm, (3H þ
2H)ꢄ2, Ph-H), 13.70 (br, s, 1Hꢄ2, NHꢄ2, NH-1 or NH-6), 13.87 (br, s, 1Hꢄ2, NHꢄ2, NH-6 or
NH-1) ppm; 13C NMR: ꢁ ¼ 125.42, 125.62, 129.10, 130.60 (C of Ph), 150.16 (C-3), 166.97 (C-5) ppm;
IR (KBr): ꢂꢀ¼ 3123 (N-H), 1464, 1550, 1600 (aromatic skeleton), 1249 (C¼S), 1380 (CH3) cmꢁ1
FAB-MS (8kV): m=z ¼ 383 (Mþ 1).
;
N,N0-Bis[5-mercapto-3-(p-methoxyphenyl)-1,2,4-triazol-4-yl]hydrazine (3d, C18H18N8O2S2)
Colorless needles; yield: 68%; mp 253–255ꢃC; 1H NMR: ꢁ ¼ 3.82 (s, 3H, CH3), 7.06–7.08, 7.84–7.86
(dd, 2Hꢄ2 each, J ¼ 9.2 Hz), 13.57 (br, s, 1Hꢄ2, NHꢄ2, NH-1 or NH-6), 13.71 (br, s, 1Hꢄ2, NHꢄ2,
NH-6 or NH-1) ppm; 13C NMR: ꢁ ¼ 55.37 (CH3), 114.53, 117.85, 127.30, 160.98 (C of Ph), 150.10
(C-3), 166.60 (C-5) ppm; IR (KBr): ꢂꢀ¼ 3129 (N-H), 1450, 1568, 1599 (aromatic skeleton), 1257
(C¼S), 1384 (CH3) cmꢁ1; FAB-MS (8kV): m=z ¼ 443 (Mþ 1).
N,N0-Bis[5-mercapto-3-(p-trifluoromethylphenyl)-1,2,4-triazol-4-yl]hydrazine
(3e, C18H12F6N8S2)
Colorless needles; yield: 73%; mp 273–274ꢃC; 1H NMR: ꢁ ¼ 7.91–7.92, 8.12–8.14 (dd, 2Hꢄ2 each,
J ¼ 8.3 Hz), 13.89 (br, s, 2Hꢄ2, NHꢄ2, NH-1 and NH-6) ppm; 13C NMR: ꢁ ¼ 122.97, 124.77, 126.11,
126.42 (C of Ph), 129.30 (CF3), 149.08 (C-3), 167.49 (C-5) ppm; IR (KBr): ꢂꢀ¼ 3134 (N-H), 1460,
1545, 1601 (aromatic skeleton), 1245 (C¼S), 1380 (CH3) cmꢁ1; FAB-MS (8kV): m=z ¼ 519 (Mþ 1).
The Preparation of Hemiacetal 5
In the above-mentioned procedure for the synthesis of 3, the solvent was displaced by dry ethanol with
several drops of conc HCL. The mixture was then stirred while refluxing for 3–4 h. The new compound
as monitored by TLC was isolated using column chromatography as a colorless oil. 1H NMR:
ꢁ ¼ 8.06–8.07, 7.64–7.66, 7.52–7.55 (m each, 2Hþ 1Hþ 2H, Ph–H), 6.99 (br, s, 1H, OH), 5.53 (s,
1H, CH), 3.79–3.84, 3.60–3.65 (qþ q each, 1H each, CH2, 2J ¼ 9.8 Hz, 3J ¼ 7.0 Hz), 1.15–1.17 (t, 3H,
J ¼ 7.0 Hz) ppm. The prochirality of the CH2 group can be observed from the above spectral data,
owing to the existence of the chiral center at the ꢀ-C; IR (neat): ꢂꢀ¼ 3423 (OH), 1692 (C¼O), 1227,
1283 (C–O) cmꢁ1
.
Acknowledgements
The authors express sincere gratitude to the Natural Science Foundation of China (No. 20572057) and
the Natural Science Foundation of Shandong Province (No. Y2003B01) for financial support.
References
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[2] Chiara BV, Maurizio M, Augusto CA, Mario G (1998) J Heterocyclic Chem 35: 29