M. Hagimori, Y. Murakami, N. Mizuyama, and Y. Tominaga
Vol 000
5-Cyano-2-(4-diethylaminophenyl)-4-methylsulfanyl-1H-
pyrimidin-6-one (5d). This compound (0.079 g, 0.3 mmol)
was prepared in 25% yield from 1 and 4-(diethylamino)
benzaldehyde (4d). Yellow needles. mp 315–318°C. IR
(KBr) ν: 3450 (OH, br), 2220 (CN), 1650, 1610, 1510,
1500 cmꢀ1. UV (EtOH) λmax nm (log ε): 319 (4.42), 368
(4.60), 414(4.74). 1H NMR (DMSO-d6) δ: 1.12 (6H, m, N-
CH2-CH3), 2.62 (3H, s, SMe), 3.44 (4H, m, N-CH2-CH3), 6.76
(2H, d, J = 9.1 Hz, 3′,5′-H), 8.14 (2H, d, J = 9.1 Hz, 2′,6′-H),
12.78 (1H, brs, NH). Ms m/z: 315 (M+ + 1, 11), 314 (M+, 47),
299 (100), 298 (24), 283 (55), 131 (29), 66 (23). Anal. Calcd.
for C16H18N4OS = 314.1201: C, 61.12; H, 5.77; N, 17.82.
Found: C, 61.12; H, 5.68; N, 17.91.
Calcd. for C18H13N3OS = 319.3814: C, 67.69; H, 4.10; N,
13.16. Found: C, 67.73; H, 4.18; N, 13.36.
5-Cyano-2-(4-dimethylaminophenyl)styryl-4-methylsulfanyl-
1H-pyrimidin-6-one (5i). This compound (0.034 g, 0.1 mmol)
was prepared in 11% yield from 1 and (E)-3-(4-(dimethylamino)
phenyl)acrylaldehyde (4i). Red brown solid. mp >300°C. IR
(KBr) ν: 3450 (OH, br), 2200 (CN), 1640, 1620, 1590, 1530,
1502 cmꢀ1. UV (EtOH) λmax nm (log ε): 257 (5.27), 455 (5.40).
1H NMR (DMSO-d6) δ: 2.66 (3H, s, SMe), 3.01 (6H, s, NMe2),
6.00 (1H, d, J= 15.5Hz, C¼CH), 6.75 (2H, d, J=8.8Hz, 3′,5′-H),
7.51 (2H, d, J= 8.8Hz, 2′,6′-H), 8.01 (1H, d, J =15.5Hz, C¼CH),
12.80 (1H, brs, NH). Ms m/z: 313 (M+ + 1, 21), 312 (M+, 99), 311
(20), 297 (18), 171 (18), 140 (13), 134 (100), 44 (15). Anal. Calcd.
for C16H16N4OS = 312.3906: C, 61.52; H, 5.16; N, 17.93. Found:
C, 61.23; H, 4.99; N, 17.90.
5-Cyano-2-(4-diphenylaminophenyl)-4-methylsulfanyl-1H-
pyrimidin-6-one (5e).
This compound (0.201 g, 0.5 mmol)
was prepared in 49% yield from 1 and 4-(diphenylamino)
benzaldehyde (4e). Yellow needles. mp 315–316°C. IR (KBr)
ν: 3450 (OH, br), 2210 (CN), 1620, 1530 cmꢀ1. UV (EtOH)
5-Cyano-4-methylsulfanyl-2-(1-naphthyl)-1H-pyrimidin-6-
one (5j). This compound (0.094 g, 0.3 mmol) was prepared in
32% yield from 1 and 1-naphthaldehyde (4j). Colorless solids.
mp 285–287°C. 1H NMR (DMSO-d6) δ: 2.56 (3H, s, SMe),
7.59–7.67 (3H, m, naphthyl-H), 7.84 (1H, d, J = 7.3 Hz,
naphthyl-H), 8.02–8.08 (1H, m, naphthyl-H), 8.16 (1H, d,
J = 8.2 Hz, naphthyl-H), 8.29–8.32 (1H, m, naphthyl-H), 12.78
(1H, brs, NH). Ms m/z: 294 (M+ + 1, 21), 293 (M+, 100), 292
(53), 278 (28), 197 (13), 154 (50), 153 (30), 140 (61), 127 (28),
104 (15). Anal. Calcd. for C16H11N3OS = 293.3442: C, 65.51;
H, 3.78; N, 14.32. Found: C, 66.07; H, 3.78; N, 13.87.
1
λmax nm (log ε): 251 (4.33), 291 (4.17), 408 (4.41). H NMR
(CDCl3) δ: 2.68 (3H, s, SMe), 7.08 (2H, d, J = 8.8 Hz, 2′,6′-H),
7.13–7.38 (10H, m, 2phenyl-H), 8.13 (2H, d, J = 8.8Hz, 3′,5′-H),
12.59 (1H, brs, NH). Ms m/z: 411 (M+ + 1, 28), 410 (M+, 100),
394 (14), 271 (31), 270 (13), 140 (14), 44 (32). Anal. Calcd.
for C24H18N4OS = 410.4921: C, 70.22; H, 4.42; N, 13.65. Found:
C, 70.50; H, 4.27; N, 13.62.
2-(4-Chlorophenyl)-5-cyano-4-methylsulfanyl-1H-pyrimidin-
6-one (5f). This compound (0.131 g, 0.5 mmol) was prepared in
47% yield from 1 and 4-chlorobenzaldehyde (4f). Slight yellow
needles. mp 309–310°C. IR (KBr) ν: 3450 (OH, br), 2210 (CN),
1680, 1600, 1580, 1540, 1520cmꢀ1. UV (EtOH) λmax nm (log ε):
256 (4.40), 301 (4.14). 1H NMR (DMSO-d6) δ: 2.68 (3H, s,
SMe), 7.64 (2H, d, J = 8.7 Hz, 3′,5′-H), 8.20 (2H, d, J = 8.7 Hz,
2′,6′-H), 12.80 (1H, brs, NH). 13C NMR (DMSO-d6) δ: 13.7,
94.9, 108.3, 129.7, 130.7, 131.4, 139.0, 158.1, 163.3, 175.9. Ms
m/z: 278 (M+ + 1, 7), 277 (M+, 40), 273 (15), 140 (100), 138
(44), 112 (17), 111 (15), 102 (12). Anal. Calcd. for
C12H8ClN3OS = 277.7302: C, 51.90; H, 2.90; N, 15.13. Found:
C, 51.85; H, 2.87; N, 15.24.
5-Cyano-2-(4-fuluorophenyl)-4-methylsulfany-1H-pyrimidin-
6-one (5g). This compound (0.091 g, 0.4 mmol) was prepared in
35% yield from 1 and 4-fluorobenzaldehyde (4g). Colorless
needles. mp 315–317°C. IR (KBr) ν: 3450 (OH, br), 2220 (CN),
1680, 1670, 1660, 1605, 1550, 1525, 1505 cmꢀ1. UV (EtOH)
λmax nm (log ε): 289 (4.28). 1H NMR (CDCl3 + CF3COOH) δ:
2.82 (3H, s, SMe), 7.83 (2H, m, phenyl-H), 8.25 (2H, m, phenyl-
H). Ms m/z: 262 (M+ + 1, 10), 261 (M+, 66), 245 (14), 140 (100),
122 (75), 121 (12), 112 (11), 95 (18). Anal. Calcd. for
C12H8FN3OS = 261.2759: C, 55.16; H, 3.09; N, 16.08. Found: C,
55.57; H, 3.02; N, 16.37.
REFERENCES AND NOTES
[1] (a) Soll, R. M.; Kenney, W. A.; Primeau, J.; Garrick, L.;
McCaully, R. J.; Colatsky, T.; Oshiro, G.; Park, C. H.; Hartupee, D.
Bioorg Med Chem Lett 1993, 3, 757; (b) Chu-Moyer, M. Y.; Ballinger,
W. E.; Beebe, D. A.; Berger, R.; Coutcher, J. B.; Day, W. W.; Li, J.;
Mylari, B. L.; Oates, P. J.; Weekly, R. M. J Med Chem 2002, 45, 511;
(c) Kim, G. T.; Ryu, E. J.; Jang, Y. J.; Lee, C. S.; Youn, H.; Cho,
Y. R.; Joo, H. Y. J Antibiot 2004, 5, 468; (d) Maring, J. G.; Groen,
H. J. M.; Wachters, F. M.; Uges, D. R. A.; de Vries, E. G. E.
Pharmacogenomics J 2005, 5, 226; (e) Amr, A. G. E.; Mohamed,
A. M.; Mohamed, S. F.; Abdel-Hafez, N. A.; Hammam, A. E. F. G. Bioorg
Med Chem 2006, 14, 5481; (f) Venu, T. D.; Khanum, S. A.; Firdouse, A.;
Manuprasad, B. K.; Shashikanth, S.; Mohamed, R.; Vishwanath, B. S.
Bioorg Med Chem Lett 2008, 18, 4409.
[2] (a) Joule, J. A.; Mills, K. Heterocyclic Chemistry, 5th ed.;
Blackwell: Oxford, 2010, 189; (b) Crosby, D. G.; Berthold, R. V. J Org
Chem 1960, 25, 1916; (c) Chhabria, M. T.; Bhatt, H. G.; Raval, H. G.;
Oza, P. M. Bioorg Med Chem Lett 2007, 17, 1022; (d) Christopherson,
R. I.; Lyons, S. D.; Wilson, P. K. Acc Chem Res 2002, 35, 961; (e) Chen, Q.;
Liu, Z. M.; Chen, C. N.; Jiang, L. L.; Yang, G. F. Chem Biodivers 2009, 6, 1254.
[3] (a) Tominaga, Y.; Matsuda, Y. J Heterocycl Chem 1985, 22,
937; (b) Tominaga, Y.; Matsuda, Y. J Synth Org Chem Jpn 1985, 43,
669; (c) Dieter, R. K. Tetrahedron 1986, 42, 3029; (d) Tominaga, Y.
J Synth Org Chem Jpn 1989, 47, 413; (e) Tominaga, Y. In Trends in
Heterocyclic Chemistry; Menon, J., Ed.; Council of Scientific Research
Integration, Research Trends: Trivandrum, 1991, Vol. 2, p 43.
[4] (a) Tominaga, Y.; Kohra, S.; Honkawa, H.; Hosomi, A. Het-
erocycles 1989, 29, 1409; (b) Kohra, S.; Tominaga, Y.; Hosomi, A.
J Heterocycl Chem 1988, 25, 959.
5-Cyano-4-methylsulfanyl-2-(4-phenylphenyl)-1H-pyrimidin-
6-one (5h).
prepared in 54% yield from
carbaldehyde (4h). Slight yellow leaflets. mp 230–232°C. IR
(KBr) ν: 3450 (OH, br), 2220 (CN), 1680, 1605, 1520 cmꢀ1
This compound (0.172 g, 0.5 mmol) was
1
and [1,1′-biphenyl]-4-
.
[5] Hirose, M.; Hagimori, M.; Shigemitsu, Y.; Mizuyama, N.
Wang, B. C.; Tominaga, Y. Heterocycles 2009, 78, 899.
[6] Yan, S.; Niu, Y.; Chen, X.; Liu, Y.; Lin, J. J Heterocycl Chem
2012, 49, 877.
[7] Tominaga, Y.; Hojo, M.; Hosomi, A. J Synth Org Chem Jpn
1992, 50, 48.
[8] He-Reddy, K.; Pa-Reddy, A.; Veeranagaiah, V. India J Chem
1992, 31, 1992.
UV (EtOH) λmax nm (log ε): 287 (4.62). 1H NMR (DMSO-
d6) δ: 2.71 (3H, s, SMe), 7.42–7.52 (3H, m, 3″,4″, 5″-H),
7.76 (2H, d, J = 7.2 Hz, 2″,6″-H), 7.86 (2H, d, J = 8.4 Hz,
2′,6′-H), 8.29 (2H, d, J = 8.4 Hz, 3′,5′-H), 12.79 (1H, brs,
NH). 13C NMR (DMSO-d6) δ: 13.7, 92.6, 115.3, 127.7,
127.8, 129.3, 129.8, 130.3, 130.5, 139.2, 145.4, 158.5,
160.7, 175.9. Ms m/z: 320 (M+ + 1, 16), 319 (M+, 69), 180
(53), 140 (100), 83 (15), 69 (19), 57 (18), 44 (50). Anal.
[9] (a) Mizuyama, N.; Tominaga, Y.; Kohra, S.; Ueda, K.;
Hirayama, S.; Shigemitsu, Y. Bull Chem Soc Jpn 2006, 79, 602;
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet