Synthesis and reactions of 2-benzoylmethyl-2-phenyl-4,6-di(phenylimino)-5h- 1,3,5-dithiazinium perchlorate

Full text of DOI:10.1023/B:RUJO.0000045913.55155.81

Russian Journal of Organic Chemistry, Vol. 40, No. 8, 2004, pp. 1222-1223. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 8, 2004,
pp. 1269-1270.
Original Russian Text Copyright Ó 2004 by Glotova, Protsuk, Dvorko, Albanov..
SHORT
COMMUNICATIONS
Synthesis and Reactions of 2-Benzoylmethyl-2-phenyl-4,6-
di(phenylimino)-5H-1,3,5-dithiazinium Perchlorate
T.E. Glotova, N.I. Protsuk, M.Yu. Dvorko, and A.I. Albanov
Faworsky Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences
Irkutsk, 664033Russia
e-mail: glotova@irioch.irk.ru
Received Apri l 5, 2004
It is known that in reactions of 2,4-dithiobiurets with
aldehydes and ketones [1, 2], phenylisocyanide dichlor-
ide [3, 4, 44-dibromo-1,3-disubstituted pyrazolin-2-ones
[5] various derivatives of 1,3,5-dithiazine and 1,3,5-tri-
azine were obtained that might be of interest as possible
biologically active compounds. We formerly by reactions
of benzoylacetylene with 2,4-dithiobiuret and its 1-mono
and 1,5-disubstituted analogs prepared new derivatives
of 1,3,5-dithiazine, 1,3,5-thiadiazine, and 1,3,5-triazine
(depending on reaction conditions and solvent used) [6].
decomposes rearranging into 3,5-dipheny;-1,2-dithiolium
perchlorate (IV). With hydrazine hydrate in ethanol at
20°C compound III afforded products of nucleophilic
substitution at C4 and C6 atoms of dithiazine ring, and
also at C2 atom of this ring and carbonyl group: 3,5-di-
phenylamino-1,2,4-triazole (V) and 3,5-diphenylpyrazole
(VI) respectively.
2-Benzoylmethyl-2-phenyl-4,6-di(phenylimino)-
5H-1,3,5-dithiazinium perchlorate (III). To a
dispersion of 1.43 g (5 mmol) of 1,5-diphenyl-2,4-di-
thiobiuret in 20 ml of glacial acetic acid at stirring was
slowly added a solution of 1.03 g (5 mmol) of 1-benzoyl-
2-phenylacetylene and 0.58 ml of 58 HClO4 in 10 ml of
glacial acetic acid. The reaction mixture was stirred for
3 h at 20°C, the precipitate was filtered off, washed with
ÀñOH and ether, and dried in a vacuum. Yield 2.28 g
(77%), light-yellow crystals, mp. 120–122°C. IR
In this work we established that 1-benzoyl-2-
phenylacetylene (I) readily reacted with 1,5-diphenyl
-
2,4-dithiobiuret (II) in glacial acetic acid in the presence
of equimolar amount of HClO4 at 20°C affording 2-benzo-
ylmethyl-2-phenyl-4,6-di(phenylimino)-5H-1,3,5-dithia-
zinium perchlorate (III) in 77% yield.
Compound III is thermally unstable: At heating in
solutions in EtOH or AcOH or in a vacuum at 135°C it
–1
spectrum, cm : 3235 (NH), 1680 (C=O), 1440–1590
3K
13K
1+3K
& 2
3K
3K &&+
2
6
6
3K
3K
B
6
6
+&O2
$F2+
'
&
&
&O2
ꢀ
ꢀ
+&O2
1+
1+
6
6
13K
1+3K
,,
3K
,
,,,
ꢀ
,9
1+ 1+
1+3K
3K+1
1
3K
3K
1+
1
1+
1
9
9,
1070-4280/04/4008-1222Ó2004 MAIK “Nauka/Interperiodica”

SYNTHESIS AND REACTIONS OF 2-BENZOYLMETHYL-2-PHENYL-4,6-...
1223
–
1
(C=C, C=N), 1040–1120 (ClO4 ). H NMR spectrum, d,
ppm: 4.86 s (2H, CH2), 7.40–8.13 m (20H, 4C6H5), 12.50
br.s (1H, NH). 13C NMR spectrum, d, ppm: 48.67 (CH2),
58.80 (C2), 123.38, 124.19, 126.27, 127.07, 127.59,
128.48, 128.80, 129.02, 129.99, 134.10, 135.76, 136.21,
138.38 (4C6H5), 165.83 (C4, C6), 194.49 (C=O). Found,
%: C 58.89; H 3.83; Cl 5.93; N 7.33; S 10.47.
C29H24ClN3O5S2. Calculated, %: C 58.63; H 4.07;
Cl 5.97; N 7.07; S 10.79.
116.70, 118.80, 120.57, 128.70, 128.92, 141.05, 142.54
(2Ph), 151.46, 158.18 (C3 and C5). Found, %: C 66.87;
H 5.08; N 27.53. C14H13N5. Calculated, %: C 66.91;
H 5.21; N 27.87.
The mother liquor after isolation of compound V was
evaporated to 1/3 of initial volume, cooled, and poured
in a 5-fold volume of water. The separated precipitate
was filtered off and dried to obtain 0.19 g (86%) of
3,5-diphenylpyrazole (VI), mp 198–199°C (publ.: mp
199–200°C [7]). 13C NMR spectrum, d, ppm: 99.62 (C4),
115.61, 116.54, 125.13, 127.45, 128.12, 128.63, 129.00,
133.69 (2Ph), 143.38 (C5), 151.34 (C3). Found, %:
C 81.57; H 5.28; N 12.53. C15H12N2. Calculated, %:
C 81.79; H 5.49; N 12.71.
3,5-Diphenyl-1,2-dithiolium perchlorate (IV). In 20
ml of boiling ÀñOH was heated 0.594 g (1 mmol) of
dithiazine III. The separated precipitate was filtered off,
washed with ether, and dried in a vacuum. Yield 0.27 g
(76% ), dark-yellow crystals, mp 222–224°C. IR
–1
spectrum, cm : 1590 (C=C in ring), 1420–1490 (C=C,
IR spectra were recorded on Specord 75IR instrument
Ph). 1H NMR spectrum, d, ppm: 7.66–8.25 m (10H,
1
from pellets with KBr. H and 13C NMR spectra
2Ph), 9.38 s (1H, CH in ring). 13C NMR spectrum
, d,
were registered on spectrometer Bruker-DPX 400
ppm: 129.29, 130.20, 130.68, 134.95 (2Ph), 133.52 (C4),
188.16 (C3 and C5). Found, %: C 51.04; H 3.37;
Cl 9.60; S 17.89. C15H11ClO4S2. Calculated, %:
C 50.77; H 3.12; Cl 9.99; S 18.07.
[400.13 MHz (1H) and 100.61 MHz (13C)] in DMSO-d6.
REFERENCES
1. Fairfull, A.E.S. and Peak, D.A., J. Chem. Soc., 1955, vol. 3,
p. 803.
2. Chande, M.S. and Shetgiri, N.P., J. Indian Chem. Soc., 1990,
vol. 67, p. 849.
3. Pathe, P.P. and Paranjpe, M.G., Indian J. Chem. Seet. B,
1981, vol. 20, p. 824.
4. Pathe, P.P. and Paranjpe, M.G., J. Indian Chem. Soc., 1984,
vol. 61, p. 149.
5. Chande, M.S., Bhandari, J.D., and Karyekar, A.S., Indian
J. Chem. Seet. B, 1995, vol. 34, p. 990.
6. Glotova, T. E., Protsuk, N. I., Albanov, A. I., Lopyrev, V. A.,
and Dolgushin, G. V., Cent. Europ. J. Chem., 2003, vol. 3,
p. 222.
Reaction of compound III with hydrazine hydrate.
To a dispersion of 0.594 g (1 mmol) of compound III in
20 ml of EtOH was added at stirring a solution of 3 ml of
hydrazine hydrate in 10 ml of EtOH, and the mixture
was stirred for 3 h at 20°C. The yellow solution was
filtered from a light suspension and maintained at 5°C
for 3 days. The separated precipitate was filtered off,
and dried to obtain 0.14 g (56%) of 3,5-diphenylamino-
1,2,4-triazole (V), colorless crystals, mp 211–212°C. IR
–1
spectrum, cm : 3290, 3380 (NH), 1490–1610 (C=C,
C=N). H NMR spectrum, d, ppm: 6.80–7.74 m (10H,
1
2Ph), 8.93 s (1H, NHPh), 9.26 s (1H, NHPh), 11.76 s
(1H, NH in ring). 13C NMR spectrum, d, ppm: 115.81,
7. Beilst, H., vol. 23, p. 253.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004