558
BRATENKO et al.
afforded in high yield 1-aryl(heteryl)-3-[1-phenyl-3-
integral intensity of each one corresponding to one
proton, and with J 2.4 3.0 Hz. Therewith the signal
in the 5.4 5.7 ppm region should be apparently
assigned to the methine proton, and the signals in the
range 3.9 4.2 and 3.2 3.4 ppm to the methylene
protons.
aryl(heteryl)-4-pyrazolyl]-3-propenones
(Table 1).
(IIIa k)
The composition and structure of the reaction
products were proved by elemental and spectral
analysis. For instance, in the IR spectra the absorp-
tion band of the carbonyl group conjugated with a
double bond and aromatic (heteroaromatic) substitu-
ents is located in the range 1660 1670 cm 1 [10].
The results of studies on the luminescence
properties of 1-phenyl-3-aryl(heteryl)-5-(4-pyrazolyl)-
2-pyrazolines will be published elsewhere.
EXPERIMENTAL
IR spectra were recorded on spectrometer UR-20
1
from KBr pellets. H NMR spectra were registered
in DMSO-d6 solutions on spectrometer Varian-
Gemini (300 MHz), internal reference TMS.
1-Aryl(heteryl)-3-[1-phenyl-3-aryl(heteryl)-4-
pyrazolyl]-3-propenones IIIa k. To a solution of
0.005 mol of aldehyde Ia d in 15 ml of 2-propanol
was added at 18 20 C while stirring 0.005 mol of
ketone IIa h, the reaction mixture was heated to
50 C, and 1 ml of 20% aqueous sodium hydroxide
was added. The mixture was stirred at 50 C for
0.5 h, then cooled to 18 20 C, and stirred for 3 h
more. The separated precipitate was filtered off and
crystallized from 2-propanol.
I, R1 = Ph (a), 2-thienyl (b), 5-methyl-2-furyl (c),
3-pyridyl (d); II, R2
=
Ph (a), 4-FC6H4 (b),
4-ClC6H4 (c), 4-BrC6H4 (d), 4-EtC6H4 (e), 4-MeOC6H4
(f), 2-furyl (g), 2-thienyl (h); III, IV, R1 = Ph: R2 =
Ph (a), 4-FC6H4 (b), 4-ClC6H4 (c), 4-BrC6H4 (d),
4-EtC6H4 (e), 4-MeOC6H4 (f), 2-furyl (g), 2-thienyl
(h); R2 = Ph: R1 = 2-thienyl (i), 5-methyl-2-furyl
(j), 3-pyridyl (k).
1-phenyl-3-aryl(heteryl)-5-(4-pyrazolyl)-2-pyr-
azolines IVa k. To a solution of 0.02 mol of
propenone IIIa k in 5 ml of acetic acid was added
0.002 mol of phenylhydrazine, and the mixture was
heated to boiling for 4 h. The reaction mixture was
cooled, the formed precipitate was filtered off,
washed with ethanol, and crystallized from acetic
acid.
Pyrazolyl vinyl ketones IIIa k react with phenyl-
hydrazine at boiling for 3 h in acetic acid to afford
1-phenyl-3-aryl(heteryl)-5-(4-pyrazolyl)-2-pyrazolines
IVa k in 41 58% yield. The compounds obtained
(Table 2) are colorless of light-yellow high-melting
crystalline substances. Their composition is proved by
REFERENCES
1
elemental analyses, and the structure by H NMR
spectra.
1. Bratenko, M.K., Chornous, V.A., and Vovk, M.V.,
Zh. Org. Khim., 2001, vol. 37, no. 4, pp. 587 590.
2. Bernand, M., Hulley, E., Molenda, J., Stochla, K.,
and Wrzeciono, U., Pharmazie, 1986, vol. 41, no. 8,
pp. 560 561.
3. Chary, T.J.M., Reddy, C.V.N., and Murthy, A.K.,
Indian J. Chem. Sect. B, 1992, vol. 31, no. 8,
pp. 495 498.
4. Elkaschef, M.A.-F., Abdel-Magein, F.M.E., and
Yassiu, S.M.A., Lieb. Ann., 1974, no. 1, pp. 37 43.
5. Chernyavichus, V.S., Odinets, A.G., Sausyn,, A.E.,
Berzinya, A.Ya., and Zolotoyabko, R.M., Khim.-
Farm. Zh., 1987, vol. 21, no. 8, pp. 959 965.
1
In the H NMR spectra of compounds IVa k the
protons of aromatic and heteroaromatic substituents
in pyrazoline and pyrazole fragments appear as a set
of multiplets in the typical for such protons region
6.6 8.6 ppm. The singlet signal of the proton in
the 5 position of the pyrazolines ring is shifted to
the region 8.1 8.3 ppm (cf. [11]) apparently due to
its shielding with the pyrazoline ring. The protons of
methylene and methine groups of the pyrazoline ring
form an asymmetric three-spin ABC-system that
1
appears in the H NMR spectrum as 12 principal lines
grouped into three doublets of doublets with an
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 4 2001
Bratenko
