M. A. Kolosov, D. A. Beloborodov, O. G. Kulyk, and V. D. Orlov
Vol 000
+
+
5
1 (36), 105 (31), 184(10) [M ]. Anal. Calcd for C H N O: C,
(MeOH); MS, m/z (%): 297 (100), 374 (85) [M ], 77(70). Anal. Calcd for
1
1 8 2
7
1.73; H, 4.38; N 15.21. Found: C, 71.75; H, 4.44; N 15.15.
2-Methoxy-2-(4-methylphenyl)methylene)malononitrile (2b). The
C H N : C, 80.19; H, 4.85; N 14.96. Found: C, 79.93; H, 5.01; N 15.23.
25 18 4
(
2-(4-Methylphenyl)-7-(4-nitrophenyl)-5-phenylpyrazolo[1,5-a]
ꢀ
yield was 7.26 g (94%), colorless plates, mp 100–103 C (MeOH);
pyrimidine-3-carbonitrile (6). The yield was 0.47 g (46%), yellow
ꢀ
1
1
prisms, mp 291–295 C (MeOH); H-NMR: 8.35–8.6 (5H, m, ArH),
H-NMR: 7.56 (2H, d, J= 8.2, ArH), 7.42 (2H, d, J= 8.4, ArH), 3.87
+
8.11–8.25 (2H, m, ArH), 7.98 (2H, d, J= 8, ArH), 7.55–7.7 (3H, m,
(
(
3H, s, OCH
83), 119 (45). Anal. Calcd for C12
Found: C, 72.98; H, 5.37; N 14.08.
(3)-Amino-3(5)-aryl-1H-pyrazole-4-carbonitriles
general procedure. Mixture of corresponding compound
22.0 mol), 50% hydrazine hydrate (2.64 mL, 26.4 mmol), water (8 mL),
and MeOH (4 mL) was heated for 1 h at water bath. After cooling, the
precipitate was filtered off and washed by MeOH–H O (2:1) mixture.
(3)-Amino-3(5)-phenyl-1H-pyrazole-4-carbonitrile (3a). The
3
), 2.39 (3H, s, CH
3
); MS, m/z (%): 198 (100) [M ], 91
ArH), 7.40 (2H, d, J= 8, ArH), 2.4 (3H, s, CH ); MS, m/z (%): 431
3
10 2
H N O: C, 72.71; H, 5.08; N 14.13.
+
(
100) [M ], 91 (30). Anal. Calcd for C26
17 5 2
H N O : C, 72.38; H, 3.97;
N 16.23. Found: C, 72.09; H, 4.09; N 16.35.
5
(3a,b),
2
Acknowledgments. We gratefully acknowledge V.V. Vashchenko
and I.V. Knyazeva (STC “Institute for Single Crystals” NAS of
Ukraine) for mass-spectra and V.I. Musatov (STC “Institute for
(
2
1
Single Crystals” NAS of Ukraine) for H-NMR spectra.
5
ꢀ
yield was 3.12 g (77%), yellowish plates, mp 205–208 C (water);
1
H-NMR: 12.17 (1H, br. s, NH), 7.7–7.9 (2H, m, CH), 7.3–7.6 (3H,
REFERENCES AND NOTES
m, CH), 6.43(2H, br. s, NH
2
); MS, m/z (%): 128 (100), 156 (20),
84 (20) [M ]. Anal. Calcd for C10 : C, 65.21; H, 4.38; N 30.42.
Found: C, 65.09; H, 4.31; N 30.56.
+
1
8 4
H N
[1] (a) Dhar, D. N. The Chemistry of Chalcones and Related Com-
pounds; Wiley: New York, 1981, 213 pp; (b) Brown, T., Holt, H. Jr., Lee,
M. Moses in Top Heterocycl Chem, 2006, Vol 2, pp 1–51; (c) Desenko, S.
M., Orlov, V. D. Azaheterocycles Based on the a,b-Unsaturated Ketones.
Folio: Kharkov, 1998, 148 pp (russ.); (d) Desenko, S. M. Chem Heterocycl
Comp 1995, 125; (e) Chebanov, V. A., Desenko, S. M., Gurley, T. W.
Azaheterocycles Based on a,b-Unsaturated Carbonyls. Springer, 2008; 212 p.
[2] (a) Troeschutz, R. Arch Pharm 1989, 322, 285; (b) Quiroga, J., Insuasty,
B., Hormaza, A., Saitz, C., Jullian, C. J Heterocycl Chem 1998, 35, 575; (c) Quiroga,
J., Cruz, S., Insuasty, B., Abonia, R., Cobo, J., Sanchez, A., Nogueraz, M., Low, J.
N. J Heterocycl Chem 2001, 38, 53; (d) Komarov, K. V., Chkanikov, N. D.,
Galakhov, M. V., Kolomietz, A. F., Fokin, A. V. J Fluor Chem 1990, 47, 59.
5
(3)-Amino-3(5)-(4-methylphenyl)-1H-pyrazole-4-carbonitrile
ꢀ
(
3b). The yield was 3.92g (90%), yellowish plates, mp 197 C
1
(water); H-NMR: 12.09 (1H, br. s, NH), 7.67 (2H, d, J =7.9, CH),
7.26 (2H, d, J= 7.9, CH), 6.43 (2H, br. s, NH ), 2.32 (3H, s, CH );
2 3
+
MS, m/z (%): 198 (100) [M ], 91 (10). Anal. Calcd for C11
C, 66.65; H, 5.08; N 28.26. Found: C, 66.49; H, 4.91; N 28.46.
,5,7-Triaryldihydropyrazolo[1,5-a]pyrimidine-3-carbonitriles
5a–f) and 7-(4-nitrophenyl)-5-phenyl-2-(4-methylphenyl)pyrazolo
1,5-a]pyrimidine-3-carbonitrile (6), general procedure. A mixture of
10 4
H N :
2
(
[
[
3] Elgemeiel, G. E. H., Riad, B. Y., Nawwar, G. A., Elgamal, S. Arch
Pharm 1987, 320, 223; (b) Elnagdi, H. E., Erian, A. W. Bull Chem Soc Jpn
990, 63, 1854; (c) Fedorova, O. V., Zhidovinova, M. S., Rusinov, G. L.,
corresponding aminopyrazole (3) (2.4 mmol), chalcone (4)(2.4 mmol),
and DMF (0.5 mL) was refluxed for 1 h. After cooling, MeOH (5 mL)
was added. The resulting precipitate was filtered off and washed
by MeOH. For analytical purposes, the products may be
recrystallized from MeOH or MeOH-DMF.
1
Ovchinnikova, I. G. Russ Chem Bull 2003, 8, 1768; (d) Abdel Khalik, M.
M. J Chem Res (S) 1997, 198; (e) Elfahham, H. A., Abdel-Galil, F. M.,
Ibraheim, Y. R., Elnagdi, M. H. J Heterocycl Chem 1983, 20, 667; (f) Quiroga,
J., Insuasty, B., Rincon, R., Larrahondo, M., Hanold, N., Meier, H. J Hetero-
cycl Chem 1994, 31, 1333; (g) Quiroga, J., Insuasty, B., Hormaza, A.,
Gamenara, D., Dominguez, L., Saldana, J. J Heterocycl Chem 1999, 36, 11;
2-(4-Methylphenyl)-5,7-diphenyldihydropyrazolo[1,5-a]pyrimidine-
3-carbonitrile (5a). The yield was 0.68 g (73%), pale yellow prisms,
(h) Orlov, V. D., Kiroga, K., Kolos, N. N., Desenko, S. M. Chem Heterocycl
ꢀ
mp 210–213 C (MeOH); MS, m/z (%): 375 (100), 311 (60), 388 (25)
Comp 1988, 7, 791; (i) Desenko, S. M., Orlov, V. D., Lipson, V. V., Shishkin,
O. V., Potehin, K. A., Struchkov, Y. T. Chem Heterocycl Comp 1993, 95; (j)
Lipson, V. V., Desenko, S. M., Shirobokova, M. G., Borodina, V. V.,
Musatov, V. I. Chem Heterocycl Comp 2005, 4, 492; (k) El-Agamey, A.-G.
A., Abdalla, S. O., Elmoghayar, M. R. H. Monatsh Chem 1984, 115, 1413.
+
[M ]. Anal. Calcd for C26
H
20
N
4
: C, 80.39; H, 5.19; N 14.42. Found:
C, 80.50; H, 5.11; N 14.55.
-(4-Methoxyphenyl)-2-(4-methylphenyl)-5-phenyldihydropyrazolo
7
[1,5-a]pyrimidine-3-carbonitrile (5b). The yield was 0.65 g (65%),
[4] (a) Chebanov, V. A., Sakhno, Y. I., Desenko, S. M., Chernenko,
ꢀ
pale yellow prisms, mp 210–211 C (MeOH); MS, m/z (%): 418 (100)
V. N., Musatov, V. I., Shishkina, S. V., Shishkin, O. V., Kappe, C. O. Tetra-
hedron 2007, 63, 1229; (b) Drizin, I., Holladay, M. W., Yi, L., Zhang, H. Q.,
Gopalakrishnan, S., Gopalakrishnan, M., Whiteaker, K. L., Buckner, S. A.,
Sullivan, J. P., Carroll, W. A. Bioorg Med Chem Lett 2002, 12, 1481;
+
[M ], 311 (25), 389 (15). Anal. Calcd for C H N O: C, 77.49; H,
27
22
4
5.30; N 13.39. Found: C, 77.50; H, 5.19; N 13.56.
5
,7-Bis(4-methoxyphenyl)-2-(4-methylphenyl)dihydropyrazolo
(c) Al-Enezi, A., Al-Saleh, B., Elnagdi, M. H. J Chem Res (S) 1997, 4.
[
1,5-a]pyrimidine-3-carbonitrile (5c).
The yield was 0.71 g
[
5] (a) Elnagdi, M. H., Sadek, K. U., Galil, F. M. A., Hassan, S. M. E.
ꢀ
(66%), pale yellow prisms, mp 182–185 C (MeOH); MS, m/z (%):
Arch Pharm 1988, 321, 851; (b) Sadek, K. U., Selim, M. A., El-Maghraby, M.
A. J Chem Eng Data 1985, 30, 514; (c) Zvilichovsky,G., David, M. J Chem
Soc Perkin Trans 1 1983, 11; (d) Popil’nichenko, S. V., Pil’o, S. G., Brovarets,
B. S., Chernega, A. N., Drach, B. S. Russ J Gen Chem 2005, 75, 1816;
+
448 (100) [M ], 447 (40). Anal. Calcd for C H N O : C, 74.98;
28 24 4 2
H, 5.39; N 12.49. Found: C, 75.10; H, 5.21; N 12.67.
-(4-Dimethylaminophenyl)-2-(4-methylphenyl)-5-phenyl-
dihydropyrazolo[1,5-a]pyrimidine-3-carbonitrile (5d). The yield
was 0.80 g (77%), pale yellow prisms, mp 197–200 C (MeOH);
MS, m/z (%): 431 (100) [M ], 146 (35). Anal. Calcd for C28
7
(e) Gavrilenko, B. B. Zhurnal Organicheskoj Khimii 1982, 1079 (russ.).
ꢀ
[6] (a) Kolosov, M. A., Orlov, V. D., Kolos, N. N., Shishkin, O. V.,
Zubatyuk, R. I. Arkivoc 2007, 16, 187; (b) Orlov, V. D., Kiroga, K.,
Kolos, N. N. Chem Heterocycl Comp 1987, 9, 997.
+
25 5
H N :
C, 77.93; H, 5.84; N 16.23. Found: C, 78.07; H, 6.10; N 16.01.
-(4-Chlorophenyl)-2-(4-methylphenyl)-5-phenyldihydropyrazolo
1,5-a]pyrimidine-3-carbonitrile (5e). Yield 0.68 g (67%), pale
[
7] (a) Hanefeld, U., Rees, C. W., White, A. J. P., Williams, D. J. J
7
Chem Soc Perkin Trans 1 1996, 1545; (b) Kraybill, B. C., Elkin, L. L.,
Blethrow, J. D., Morgan, D. O., Shokat, K. M. J Am Chem Soc 2002, 124,
12118; (c) Craboyes, H., Jaffe, G. E., Pachter, I. J., Rosenbloom, J. P., Vil-
lani, A. J., Wilson, J. W., Weinstock, J. J Med Chem 1968, 568; (d) Bontems,
R. J., Anderson, J. D., Smee, D. F., Jin, A., Alaghamandan, H. A., Sharma, B.
S., Jolley, W. B., Robins, R. K., Cottam, H. B. J Med Chem 1990, 33, 2174.
[
ꢀ
+
yellow prisms, mp 242 C (MeOH); MS, m/z (%): 422 (100%) [M ],
11 (98). Anal. Calcd for C26 19ClN : C, 73.84; H, 4.53; N 13.25.
Found: C, 73.99; H, 4.40; N 13.41.
3
H
4
2
,5,7-Triphenyldihydropyrazolo[1,5-a]pyrimidine-3-carbonitrile
[8] (a) Shen, Q., Huang, W., Wang, J., Zhou, X. Org Lett 2007, 9(22),
ꢀ
(
5f). The yield was 0.52 g (58%), pale yellow prisms, mp 223–224 C
4491; (b) Southwick, P. L., Dhawan, B., J Heterocycl Chem 1975, 12, 1199.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet