NEW TRANSFORMATIONS OF THE REACTION PRODUCT
1333
2
N-Benzoyl-p-nitrocynnamamide (VIII). A mix-
ture of 0.001 mol of ylide V, 0.001 mol of p-nitro-
benzaldehyde, and 15 ml of benzene was refluxed for
3 h and then left to stand for 3 h at 20 25 C. A pre-
cipitate formed and was filtered off and crystallized
from benzene. H NMR spectrum (CDCl3), , ppm:
7.04 8.30 m (11H, C6H4, C6H5, CH=CH), 8.86 br.s
(1H, NH).
spectrum (DMSO-d6), , ppm: 5.91 d (2H, JHP
13.2 Hz), 7.60-8.23 m (25H, 5C6H5).
5-Methyl-1,3-diphenyl-1,3,4-triazole (XIV). To a
solution of 0.001 mol of phosphonium salt XII in
10 ml of methanol, a solution of 0.003 mol of sodium
hydroxide in 3 ml of water was added. The resulting
mixture was heated for 0.5 h at 60 C, the methanol
was removed in a vacuum, and compound XV was
purified by recrystallization of methanol, yield 76%,
mp 80 C. This sample occurred to be identical to the
condensation product of N-benzoylphenylhydrazine
with acetamide [10]. The product was identified by
the mixed-sample test, IR spectra, and melting point
of the picrate (184 186 C) obtained after recrystalliza-
tion from ethanol. The picrate of the 3-methyl-1,5-di-
phenyl-1,2,4-triazole isomer melts at 152 154 C [10].
1
(2,4-Dichloro-4-phenyl-3-aza-1,3-butadien-1-yl)-
triphenylphosphonium chloride (X). A mixture of
0.001 mol of phosphonium salt VI, 0.03 mol of phos-
phorus pentachloride, and 20 ml of chlorobenzene was
refluxed for 1 h, cooled to 20 25 C, and sulfur di-
oxide was passed through the solution to remove
excess phosphorus pentachloride. The solution was
reduced by half in a vacuum, diluted with 30 ml of
diethyl ether, and 4.5 g of an oily substance was
separated. It was kept for 2 h at 70-80 C in an oil-
pump vacuum and used in further transformations
without additional purification.
5-Methyl-2,4-diphenyl-1,3,5-triazine (XV) was
obtained similarly to compound XIV by alkaline
cleavage of phosphonium salt XIII, yield 68%, mp
109 110 C (from ethanol). Mixed sample of this
compound and authentic 6-methyl-2,4-diphenyl-1,3,5-
triazine [11] gave no depression melting point depres-
sion. The IR spectra of these samples, too, were
identical.
(3-Phenyl-1,2,4-triazol-5-ylmethyl)triphenyl-
phosphonium perchlorate (XI). To a solution of
0.002 mol of crude phosphonium salt X in 10 ml of
THF, 0.007 mol of hydrazine hydrate was added
under cooling with an ice-cold water. The resulting
mixture was stirred for 24 h at 20 25 C, the preci-
pitate was filtered off, and the solvent was removed
in a vacuum. The residue was dissolved in 10 ml of
methanol, and 2 ml of saturated aqueous sodium per-
chlorate was added. A precipitate formed and was
REFERENCES
1. Brovarets V.S., Zyuz’ K.V., Bydzhak, R.N., Vinogra-
dova, T.K., and Drach, B.S., Zh. Obshch. Khim., 1994,
vol. 64, no. 10, p. 1642.
1
2. Brovarets, V.S., Zyuz’, K.V., Romanenko, E.A.,
and Drach, B.S., Zh. Obshch. Khim., 1995, vol. 65,
no. 12, p. 1972.
filtered off and purified by recrystallization. H NMR
2
spectrum (DMSO-d6), , ppm: 5.47 d (2H, CH2, JHP
13.6 Hz), 7.59-8.05 m (20H, 4C6H5), 9.98 s (1H,
NH).
3. Johnson, A.W., Ylides and Imines of Phosphorus,
New York: Wiley, 1993, p. 48.
(1,3-Diphenyl-1,2,4-triazol-5-ylmethyl)triphenyl-
phosphonium perchlorate (XII) was prepared si-
milarly to compound XI using phenylhydrazine in-
stead of hydrazine hydrate. 1H NMR spectrum
(DMSO-d6), , ppm: 5.76 d (2H, JHP 18.2 Hz), 7.40
7.95 m (25H, 5C6H5).
4. Naumov, V.A. and Vilkov, L.V., Molekulyarnye
struktury fosfororganicheskikh soedinenii (Molecular
Structures of Organophosphorus Compounds),
Moscow: Nauka, 1986.
2
5. Burke-Laing, M. and Laing, M., Acta Crystallogr.,
Sect. B, 1976, vol. 32, no. 12, p. 3216.
(2,4-Diphenyl-1,3,5-triazin-6-ylmethyl)triphenyl-
phosphonium perchlorate (XIII). To a solution of
crude phiosphonium salt (X) in 10 ml of THF,
0.002 mol of benzamidine hydrochloride and
0.007 mol of triethylamine were added. The resulting
mixture was stirred for 48 h at 20 25 C, the triethyl-
amine hydrochloride was filtered off, and the solvent
was removed from filtrate in a vacuum. The residue
was dissolved in 10 ml of ethanol, and 2 ml of sa-
turated aqueous sodium perchlorate was added. A
precipitate formed and was filtered off, washed with
water, and purified by recrystallization. 1H NMR
6. Brovarets, V.S., Zyuz’, K.V., Vydzhak, Z.N., Roma-
nenko, E.A., and Drach, B.S., Zh. Obshch. Khim.,
1994, vol. 64, no. 10, p. 1747.
7. Brovarets, V.S., Dopov. Nats. Akad. Navuk Ukrainy,
1998, no. 1, p. 167.
8. Drach, B.S., Kovalevm, D.A., and Kirsanov, A.V.,
Zh. Org. Khim., 1976, vol. 12, no. 3, p. 673.
9. Drach, B.S. and Kovalev, V.A., Zh. Org. Khim., 1976,
vol. 12, no. 11, p. 2319.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 9 2004