950
VYZHDAK et al.
to stand for 24 h at 20 2 C, volatile compounds were
removed in a vacuum, the residue was treated with
water and diethyl ether (2.5 ml), the ether solution
was dried for 12 h of sodium sulfate, and the solvent
was removed in a vacuum to obtain aldehydes VIIa
VIIc as a thick yellowing buttery oily materials that,
by TLC data, contained the main substance and a little
admixtures. The aldehyde group in compounds VIIa
stand for 12 h at 20 25 C, the precipitate was filtered
off, washed with THF, and suspended in 15 ml of
ethanol. The suspension was heated under reflux for
1 h, treated while hot with 1 ml of 25% aqueous
ammonia, cooled, and the precipitate was filtered off.
3-Methyl(benzyl)-5-[5-morpholino(piperidino)-
4-tosyl-1,3-oxazol-2-yl]methylenerhodanines XIa,
XIb, XId, and XIe. a. N-Methyl- or N-benzyl-
rhodanine, 0.005 mol, was added to a solution of
0.005 mol of aminal VIa or VIb in 10 ml of glacial
acetic acid. The mixture was heated to boiling, treated
with 0.1 ml of monoethanolamine, and then slowly
cooled. The precipitate was filtered off and washed
with acetic acid and ethanol.
VIIc was identified by the IR spectra:
1720 cm , CH2Cl2).
1700
C=O
1
5-Morpholino(piperidino, dimethylamino)-4-
tosyl-1,3-oxazol-2-carbaldehydes VIIIa VIIIc.
a. Acetic acid, 1 ml, phenylhydrazine, 1 ml, and 5 ml
of water were added to a solution of 0.005 mol of
aminal VIa VIc in 10 ml of ethanol. The mixture was
heated to boiling, allowed to stand for 2 h at 20 25 C,
and the precipitate was filtered off and washed with
aqueous ethanol.
b. N-Methylrhodanine, 0.005 mol, was added to a
solution of 0.005 mol of aldehyde VIIb in 10 ml of
acetic acid. Further treatment was performed as
described in procedure a. Mixed sample of XIb ob-
tained by procedures a and b gave no melting point
b. Phenylhydrazine, 0.2 ml, was added to a solu-
tion of 0.001 mol of aldehyde VIIa or VIIc in 3 ml
of ethanol, the mixture was heated to boiling, allowed
to stand for 1 h at 20 25 C, and the precipitate was
filtered off. Mixed sample of VIIIa and two samples
of VIIIc obtained by procedures a and b gave no
melting point depression.
1
depression. The H NMR spectra of the two samples
were identical.
1,3-Dimethyl-5-(5-morpholino-4-tosyl-1,3-oxa-
zol-2-yl)methylenebarbituric acid (XII). a. 1,3-Di-
methylbarbituric acid, 0.005 mol, and 0.1 ml of mono-
ethanolamine were added to a solution of 0.005 mol
of aminal VIa in 15 ml of glacial acetic acid. The
mixture was heated for 1 h at 100 C, cooled, and the
precipitate was filtered off.
5-Morpholino(piperidino)-4-tosyl-1,3-oxazol-2-
carbaldehyde thiosemicarbazones (IXa and IXb).
a. A mixture of 0.005 mol of aminal VIa or VIb,
0.005 mol of thiosemicarbazide, 1 ml of acetic acid,
and 15 ml of ethanol was heated under reflux for 0.5
h until precipitate formation began, after which it was
left to stand for 12 h at 20 25 C, and the precipitate
was filtered off.
b. 1,3-Dimethylbarbituric acid, 0.005 mol, and
0.1 ml of monoethanolamine were added to a solution
of 0.005 mol of aldehyde VIIa in 15 ml of glacial
acetic. Further treatment was performed as described
b. A mixture of 0.002 mol of aldehyde VIIb,
0.002 mol of thiosemicarbazide, and 10 ml of ethanol
was heated under reflux for 0.5 h until precipitate
formation began, after which it was left to stand for
12 h at 20 25 C, and the precipitate was filtered off
and recrystallized. Mixed sample of IXb obtained by
procedures a and b gave no melting point depression.
1
in procedure a. The H NMR spectra of the samples
of XII obtained by procedures a and b were identical.
REFERENCES
1. Chervonyi, V.A., Kharchenko, A.V., and Drach, B.S.,
Zh. Org. Khim., 1988, vol. 24, no. 2, p. 453.
5-Morpholino(piperidino)-4-tosyl-1,3-oxazol-2-
carbaldehyde N -(4-phenyl-1,3-thiazol-2-yl)hydra-
zones Xa and Xb. Bromoacetophenone, 0.002 mol,
was added to a suspension of 0.002 mol of thiosemi-
carbazone IXa or IXb in 15 ml of ethnol. The mixture
was heated under reflux for 4 h, cooled, and the pre-
cipitate was filtered off.
2. Chervonyi, V.A., Kharchenko, A.V., and Drach, B.S.,
Ukr. Khim. Zh., 1991, vol. 57, no. 4, p. 415.
3. Chervonyi, V.A., Seferov, S.O., Zyabrev, V.S., Khar-
chenko, A.V., and Drach, B.S., Dokl. Akad. Nauk
USSR, 1991, no. 11, p. 105.
4. Kharchenko, A.V., Seferev, S.O., Zyabrev, V.S.,
Chervonyi, V.A., Vdovenko, S.I., and Drach, B.S.,
Ukr. Khim. Zh., 1993, vol. 59, no. 6, p. 637.
5-Morpholino-4-tosyl-1,3-oxazol-2-carbaldehyde
N -[4-(acetylamino)-1,3-thiazol-2-yl)hydrazone
(Xd). N-(1-Chlorophenacyl)acetamide [10], 0.002 mol,
was added to a solution of 0.002 of thiosemicarbazone
IXa in 25 ml of THF. The mixture was allowed to
5. Kharchenko, A.V., Dopov. Nats. Akad. Navuk Ukraini,
1999, no. 1, p. 161.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005
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