PAPER
Studies on Phosphoroheterocycle Chemistry II
2449
agent (2 mmol). The mixture was warmed up and stirred at reflux
for 5 h. After removal of the precipitate by filtration from the reac-
tion mixture, the solvent was evaporated on a rotary evaporator un-
der reduced pressure. The resulting residue was chromatographed
on a silica gel column with a mixture of EtOAc petroleum ether
(1:3, v/v) as eluent to yield the desired compound. The pure product
was obtained by recrystallization from a mixture of CH2Cl2 petro-
leum ether.
FTIR (KBr): 3308 (N–H), 1590, 1560, 1498 (C=C), 1435, 1258 (N–
C=S), 1110 (Ar–O–C), 628 (P=S) cm–1
.
1H NMR (DMSO-d6/TMS): = 2.39 (s, 3 H, CH3), 3.80 (s, 3 H,
4
3
OCH3), 7.08 (dd, 2 H, JP–H = 2.50 Hz, JH–H = 8.24 Hz, Ar–H),
3
3
7.50 7.62 (m, 5 H, Ph H), 7.83 (dd, 2 H, JP–H = 9.80 Hz, JH–
H = 8.24 Hz, Ar–H), 10.75 (br, 1 H, NH).
31P NMR (DMSO-d6/85% H3PO4): = 59.81 ppm.
MS(EI): m/z (%) = 432 (M+, 51), 417 (51), 309 (7), 139 (10), 108
(9), 78 (65), 63 (100), 45 (30).
4a: colorless crystal, mp: 164 167 ºC, yield: 72.3%.
IR (KBr): 3263(N–H), 1593, 1577, 1499, 1453(C=C), 1386,
1
Anal. Calcd for C18H17N4OPS3 (FW = 432): C, 50.00; H, 3.94; N:
12.96. Found: C, 49.74; H, 3.88; N, 12.78.
1250(C=S), 1109(Ar–O–C) cm .
1H NMR (CDCl3/TMS): = 1.67 2.17 (m, 6 H, cyclopentyl),
2.42 2.71 (m, 2 H, cyclopentyl), 3.85 (s, 3 H, OCH3), 6.94 (dd, 2
4
3
3
H, JP–H = 2.99 Hz, JH-H = 8.48 Hz, Ar-H), 7.83 (dd, 2 H, JP–
Acknowledgement
H = 8.69 Hz, 3JH–H = 8.48 Hz, Ar H), 8.17 (br, 1 H, NHC=S).
We would like to thank Prof. HongGen Wang and his assistant
XueBing Leng for X-ray diffraction studies. Thanks also to Dr. Jun-
Min Huang for helpful discussions.
31P NMR (CDCl3/85% H3PO4): = 70.86 ppm.
MS(EI): m/z (%) = 312 (M+, 100), 279 (54), 253 (73), 220 (92), 170
(94), 83 (98), 63 (62).
Anal. Calcd for C13H17N2OPS2 (FW = 312): C, 50.00; H, 5.45; N,
8.97. Found: C, 49.87; H, 5.20; N, 8.78.
References
(1) Mulliez, M.; Wakoselman, M. Synthesis 1977, 478.
(2) Golslobov, Y. G.; Nesterova, L. I. Zh. Obshch. Khim. 1980,
50, 683.
(3) Jacobsen, N.; Bartlett, E.; Paul, A. J. Am. Chem. Soc. 1983,
105, 1613.
(4) Mulliez, M. Bull. Soc. Chim. 1985, 6, 1211.
(5) Korshin, E. E.; Eliseenkova, R. M.; Zyablikova, T. A.;
Zakharova, L. G.; Akhmadullin, A. G.; Nusmovich, V. D.;
Levin, Y. A. Izv. Akad. Nauk, Ser. Khim. 1993, 6, 1116.
(6) Deng, S. L.; Chen, R. Y.; Yang, X. F. Chemical Journal of
Chinese Universities 2000, 21, 1679.
(7) Deng, S. L.; Chen, R. Y. Chinese J. Struct. Chem. 2000, 19,
271.
(8) Chen, R. Y.; Li, C.; Wang, H.; Yao, X. Chinese Journal of
Structural Chemistry 1991, 10, 52.
(9) He, L. N.; Chen, R. Y.; Zhou, J. Chinese Journal of
Structural Chemistry 1997, 16, 215.
(10) He, L. N.; Chen, R. Y. Phosphorus, Sulfur, Silicon Relat.
Elem. 1997, 129, 111.
4b: colorless crystal, mp: 205 207 ºC, yield: 69.6%.
1H NMR (CDCl3/TMS): = 1.36 2.32 (m, 10 H, cyclohexyl), 3.84
(s, 3 H, OCH3), 6.94 (dd, 2 H, 4JP–H = 2.87 Hz, 3JH–H = 8.49 Hz, Ar–
3
3
H), 7.85 (dd, 2 H, JP–H = 8.62 Hz, JH–H = 8.49 Hz, Ar–H), 8.15
(dbr, 1 H, 2JP–H = 20 Hz, NHC=S).
31P NMR (CDCl3/85% H3PO4): = 70.87 ppm.
MS(EI): m/z (%) = 326 (M+, 55), 293 (32), 267 (22), 234 (39), 170
(34), 155 (36), 97 (100), 63 (32).
Anal. Calcd for C14H19N2OPS2 (FW = 326): C, 51.53; H, 5.83; N,
8.59. Found: C, 51.69; H, 6.05; N, 8.47.
4c: colorless crystal, mp: 215 218 ºC, yield: 64.2%.
1H NMR (CDCl3/TMS): = 1.43 2.54 (m, 11 H, cycloheptyl),
3.08 3.20 (m, 1 H, cycloheptyl) 3.85 (s, 3 H, OCH3), 6.95 (dd, 2 H,
4JP–H = 3.03 Hz, 3JH–H = 8.57 Hz, Ar H), 7.86 (dd, 2 H, 3JP–H = 8.34
Hz, 3JH–H = 8.57 Hz, Ar H), 7.95 (br, 1 H, NHC=S).
31P NMR (CDCl3/85% H3PO4): = 71.01 ppm.
(11) He, L. N.; Zhuo, R. X.; Chen, R. Y.; Li, K.; Zhang, Y. J.
Heteroatom Chemistry 1999, 10, 105.
(12) Pederson, B. S.; Lawesson, S. O. Tetrahedron 1979, 35,
2433.
MS(EI): m/z (%) = 340 (M+, 20), 177 (100), 161 (78), 149 (53), 121
(33), 91 (20), 57 (20), 18 (27).
Anal. Calcd for C15H21N2OPS2 (FW = 340): C, 52.94; H, 6.18; N,
8.24. Found: C, 52.87; H, 5.99; N, 8.21
(13) Testa, M. G.; Perrini, G.; Chiacchio, U.; Corsaro, A.
Phosphorus, Sulfur, Silicon Relat. Elem. 1994, 86, 75.
(14) Pedersen, B. S.; Scheibye, S.; Nilsson, N. H.; Lawesson, S.
O. Bull. Soc. Chim. Belg. 1978, 87, 223.
(15) (a) Biltz, H.; Slotta, K. J. Prakt. Chem. 1926, 113, 241.
(b) Biltz, H.; Slotta, K. J. Prakt. Chem. 1926, 113, 249.
(c) Biltz, H.; Slotta, K. J. Prakt. Chem. 1926, 113, 251.
(16) Tiemann, F.; Friendländer, L. Ber. 1881, 14, 1970.
(17) Knoevenagel, E.; Mercklin, E. Ber. 1904, 37, 4089.
(18) Morris, F.; Richard, B. H. J. Am. Chem. Soc. 1960, 82, 696.
(19) Jenni, J.; Kuhne, H.; Prijs, B. Helv. Chim. Acta. 1962, 45,
1163.
5-Amino-4-cyano-3-methylthia-1-phenylpyrazole (5)21
5-Methylthia-7-phenyl-2-(p-methoxyphenyl)-2,3-dihydro-
pyrazolo[4’,5’-e]-1,3,2- diazaphosphorine-4-(1H)-thione 2-
sulfide (6)
To a 50 mL three necked flask containing anhyd toluene (20 mL)
was added compound 5 (0.22 g, 0.95 mmol) and Lawesson’s re-
agent (0.193 g, 0.48 mmol). The mixture was refluxed with stirring.
During this period the starting materials dissolved slowly until the
solution became clear and then the product began to appear as a sol-
id. The reaction was complete in about 2 h. The product was filtered
and washed with a small amount of hot toluene (3 5 mL) and Et2O
(10 mL).
(20) Kandell, J. D.; Duffin, G. F. Brit. 1956, 191, 749.
(21) Tominaga, Y.; Honkawa, Y.; Hara, M.; Hosomi, A. J.
Heterocycl. Chem 1990, 27, 775.
Mp: 173 175 ºC, yield: 0.24 g (58.11%).
Synthesis 2001, No. 16, 2445–2449 ISSN 0039-7881 © Thieme Stuttgart · New York