S. N. Mikhaylichenko et al. / Tetrahedron Letters 50 (2009) 2505–2508
2507
O
O
O
O
LDA
CH3
+
Cl
R4
R4
R3
R3
Scheme 3. Synthesis of arylsubstituted 1,3-diones.
out whose support this research was impossible to complete. We
also would like to thank Dr. Alan J. Lough, PhD, Director of X-ray
Facility, Department of Chemistry University of Toronto, for his
help in obtaining the X-ray data.
Supplementary data
The physico-chemical characteristics and some X-ray data for
the new compounds (Supplementary data Tables 1, 1a, 2, and 3)
as well as experimental part could be found in the supplementary
data. CCDC 715781 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge via
quest@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallo-
graphic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK;
fax: +44 1223 336033. Supplementary data associated with this
article can be found, in the online version, at doi:10.1016/
References and notes
Figure 1. Crystal structure of compound IIIc.
1. (a) Smolin, E.; Rappoport, L. In s-Trizine and Derivatives; Interscience: NY, 1959;
p
664p; (b) Pogosyan, G.; Pankratov, V.; Zaplishny, V.; Matsoyan, S. In
Polytriazines; Korshak, V., Ed.; Armenian SSR Academy of Sciences Publishing
House: Erevan, 1987; p 615p.
To study the fine structure of the resulting pyrazolyl-triazines,
we carried out X-ray diffraction for compound IIIc whose crystals
were grown from an iso-propanol/water mixture. The projection
of the three-dimensional structure of the derivative IIIc is shown
in Figure 1. Selected interatomic distances and bond angels are gi-
ven in Tables 2 and 3, respectively. The complete tables of aromatic
coordinates, thermal parameters, bond lengths, and bond angles
were deposited with the Cambridge Structural Database.
2. (a) Chesnyuk, A.; Mikhaylichenko, S.; Zavodnov, V.; Zaplishny, V. Chem.
Heterocycl. Compd. 2002, 2, 197–203; (b) Mikhaylichenko, S.; Chesnyuk, A.;
Zavodnik, V.; Firgang, S.; Konyushkin, L.; Zaplishny, V. Chem. Heterocycl. Compd.
2002, 3, 326–334; (c) Mikhaylichenko, S.; Chesnyuk, A.; Konyushkin, L.;
Zaplishny, V. Russ. Chem. Bull., Int. Ed. 2003, 5, 1–4; (d) Chesnyuk, A.;
Mikhaylichenko, S.; Konyushkin, L.; Firgang, S.; Zaplishny, V. Russ. Chem. Bull.,
Int. Ed. 2005, 8, 1–7; (e) Mikhaylichenko, S.; Chesnyuk, A.; Konyushkin, L.;
Zaplishny, V. Chem. Heterocycl. Compd. 2006, 5, 731–737; (f) Chesnyuk, A.;
Mikhaylichenko, S.; Zaplishny, V.; Konyushkin, L.; Firgang, S. Chem. Heterocycl.
Compd. 2008, 3, 339–348.
3. (a) Mikhaylichenko S.; Chesnyuk A.; Firgang S.; Kotlyarov N.; Zaplishny V.
Patent RU 2,230,063, 2004; Chem. Abstr. 2004, 141, 225541.; (b)
Mikhaylichenko S.; Chesnyuk A.; Dmitrieva I.; Kotlyarov N.; Zaplishny V.
Patent RU 2,230,065, 2004; Chem. Abstr. 2004, 141, 225543.; (c)
Mikhaylichenko S.; Chesnyuk A.; Dmitrieva I.; Kotlyarov N.; Zaplishny V.
Patent RU 2,232,160, 2004; Chem. Abstr. 2004, 141, 243570.; (d)
Mikhaylichenko S.; Chesnyuk A.; Dmitrieva I.; Suslov A.; Kotlyarov N.;
Zaplishny V. Patent RU 2,230,066, 2004; Chem. Abstr. 2004, 141, 225544.; (e)
Chesnyuk A.; Mikhaylichenko S.; Konyushkin L.; Kotlyarov N.; Zaplishny V.
Patent RU 2,265,604, 2005; Chem. Abstr. 2005, 144, 22947.; (f) Chesnyuk A.;
Mikhaylichenko S.; Firgang S.; Kotlyarov, N.; Zaplishny V. Patent RU 2,273,130,
2006; Chem. Abstr. 2006, 144, 345097.; (g) Chesnyuk A.; Mikhaylichenko S.;
Konyushkin L.; Kotlyarov N.; Zaplishny V. Patent RU 2,273,131, 2006; Chem.
Abstr. 2006, 144, 345098.
4. (a) Mikhaylichenko S.; Chesnyuk A.; Konyushkin L.; Kotlyarov N.; Zaplishny V.
Patent RU 2,233,837, 2004; Chem. Abstr. 2004, 141, 260775.; (b)
Mikhaylichenko S.; Chesnyuk A.; Demchenko M.; Tarasov V.; Kotlyarov N.;
Zaplishny V. Patent RU 2,235,093, 2004; Chem. Abstr. 2004, 141, 260777.
5. (a) Mikhaylichenko, S.; Chesnyuk, A.; Konyushkin, L.; Firgang, S.; Kotlyarov,
N.; Zaplishny, V. Patent RU 2,189,983, 2002; Chem. Abstr. 2002, 139, 214492.;
(b) Mikhaylichenko, S.; Chesnyuk, A.; Tarasov, V.; Konyushkin, L.; Kotlyarov,
N.; Zaplishny, V. Patent RU 2,200,160, 2003; Chem. Abstr. 2003, 140, 199350.;
(c) Mikhaylichenko, S.; Chesnyuk, A.; Usov, V.; Deviatkin, A.; Kotlyarov, N.;
Zaplishny, V. Patent RU 2,203,895, 2003; Chem. Abstr. 2003, 140, 252672.; (d)
Mikhaylichenko, S.; Chesnyuk, A.; Abehtikova, O.; Ignatova, T.; Deviatkin, A.;
Kotlyarov, N.; Zaplishny, V. Patent RU 2,239,650, 2004; Chem. Abstr. 2004,
141, 397255.; (e) Mikhaylichenko, S.; Chesnyuk, A.; Abehtikova, O.;
Kotlyarov, N.; Zaplishny, V. Patent RU 2,248,972, 2005; Chem. Abstr. 2005,
142, 316866.
The pyrazolyl-triazine ring system in moleculeIIIc is mainly pla-
nar. As can be seen from Table 2, the bond lengths in the triazine
ring are slightly distorted and vary from 1.356 (N(1)–C(2)) to
1.318 (N(3)–C(3)), which is somewhat different from the bond
0
lengths in non-substituted s-triazines.15–19 (1.337 ÅA). The 1,3,5-tri-
azine ring is unsymmetrical with the bond angles (see Table 3) at
the nitrogen atoms in the ring are distorted (112.72° (N(1))–
114.67° (N(2)) and differ substantially from the bond angels at
the carbon atoms (125.22° (C(3))–129.03° (C(1)). The bond lengths
and angles of the pyrazole ring are slightly different from the non-
0
substituted pyrazole ring. The C(14)–N(6) (1.378 ÅA) and N(6)–N(7)
(1.380 Å) are longer than the same bonds in non-substituted pyra-
zole ring (1.356 and 1.365 Å, respectively).17 This is probably due to
the conjugation with the 1,3,5-triazine ring. The bond angels vary
from 105.2° (N(7)) to the 110.6° (C(16)) and this is close to the angle
values of the unsubstituted pyrazole. Both piperidine rings have a
chair conformation, and the bond lengths and angles agree well
with the average values observed in cyclic nonaromatic amines.
In summary, a series of new 1,3,5-triazine derivatives contain-
ing the pyrazole fragment and triazine ring together with high bio-
activity potential have been prepared.
Acknowledgments
6. (a) Mikhaylichenko, S.; Chesnyuk, A.; Chenikov, I.; Yasian, U.; Zaplishny, V.
Patent RU 2,187,504, 2002; Chem. Abstr. 2002, 139, 150494.; (b)
Mikhaylichenko, S.; Chesnyuk, A.; Konyushkin, L.; Zaplishny, V. Patent RU
2,187,505, 2002; Chem. Abstr. 2002, 139, 150495.
We would like to thank the Chairman of the Physical and Envi-
ronmental Department of UTSC Professor Donald E. Cormack with-