Activity of 3-hydrazino-1,2,4-triazines in reaction with N,N-dimethylcarbamoyl bromide

Full text of DOI:10.1134/S1070428010110254

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 11, pp. 1750−1751. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © L.M. Mironovich, M.A. Ivanov, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 11, pp. 1739−1740.
SHORT
COMMUNICATIONS
Activity of 3-Hydrazino-1,2,4-triazines in Reaction
with N,N-Dimethylcarbamoyl Bromide
L. M. Mironovicha and M. A. Ivanovb
aSumy State University, Sumy, Russia
bEngelgardt Institute of Molecular Biology, Russian Academy of Sciences, Moscow, 119991 Russia
e-mail: ivanovma73@mail.ru
Received April 6, 2010
DOI: 10.1134/S1070428010110254
The synthesis of new derivatives of 1,2,4-triazines is
interesting both from the theoretical and practical view-
point due to the wide range of the biological activity of
compounds from the 1,2,4-triazine series [1]. Published
description exists of the preparation of fused systems
underlain by the substituted 3-hydrazino-1,2,4-triazines
treated with various acylating agents. It was established
that the heterocyclization of compounds under consider-
ation proceeded at the N2 atom of the triazine ring provid-
ing the derivatives of [1,2,4]triazolo[4,3-b][1,2,4]-triazine
and not [1,2,4]triazolo[4,3-c][1,2,4]triazine [1, 2].
Depending on the nature of the substituent in the po-
sition 6 of initial compounds I and II the acylation with
the N,N-dimethylcarbamoyl bromide led to the formation
of compounds of different chemical nature: 3-dimethyl-
amino-6-phenyl-1,7-dihydro[1,2,4]triazolo[4,3-b][1,2,4]
triazin-7-one (III) and N1-dimethyl-aminocarbonyl-N-
(6-tert-butyl-3-hydrazino-4,5-dihydro-1,2,4-triazin-5-
one) (IV). The difference in the acylation products is
presumably due to the high solubility of compound II.
But more probably the course of the reaction is affected
by dissimilar electron density distribution in initial com-
pounds I and II. The structure of products obtained was
derived from the combined data of the elemental analy-
sis, IR, 1H NMR, and mass spectra. The IR spectrum of
compound IV contains a characteristic absorption band of
the carbonyl group of the N,N-dimethylcarbamoyl residue
at 1710 cm–1 lacking in the spectra of compounds I–III.
We carried out the acylation of 3-hydrazinotriazines
with N,N-dimethylcarbamoyl bromide aiming at the
preparation of new derivatives and bicyclic systems of
the 1,2,4-triazine series.
The selected objects of the study were 3-hydrazino-
6-R-4,5-dihydro-1,2,4-triazin-5-ones I, II obtained by
treating with hydrazine 3-thioxo-6-R-2,3,4,5-tetranydro-
1,2,4-triazin-5-ones in alcohol by procedures [3] [(I), mp
222–223°C] and [4] [(II), mp 270–271°C].
3-Dimethylamino-6-phenyl-1,7-dihydro[1,2,4]-
triazolo[4,3-b][1,2,4]triazin-7-one (III). To a dispersion
of 0.203 g (1 mmol) of 4,5-dihydro-1,2,4-triazin-5-one І
O
O
O
O
H
O
N
N
R
N
Bu-t
Me2N
Br
Me2N
R = Ph
Br
HN
HN
N
H
H2N
N
Me2N
R = t-Bu
N
N
N
Ph
N
N
N
N
NMe2
H
H
O
III
I, II
IV
R = Ph (I), t-Bu (II).
1750

ACTIVITY OF 3-HYDRAZINO-1,2,4-TRIAZINES IN REACTION
1751
in 10 ml of DMF was added at stirring 0.22 g (1.5 mmol)
of N,N-dimethylcarbamoyl bromide. The mixture was
stirred at 70–80OC over 4.5–5 h. On cooling the reac-
tion mixture was filtered and diluted with distilled water
(1 : 3), the separated precipitate was filtered off, dried in
air, and recrystallized from 2-propanol. Yield 0.2 g (78%),
white crystals, mp 245–246°C (i-PrOH). IR spectrum, ν,
cm–1: 3156, 3064, 2988, 2920, 1680, 1580, 1564, 1520,
1444, 1328, 1312, 1260, 1252, 1156, 1076, 996, 892, 816,
788, 756, 700, 684, 564. 1H NMR spectrum (DMSO-d6),
δ, ppm: 1.51 s (6H, Me), 7.40–7.90 m (5H, Ph), 13.20 s
(1H, NH). Found, %: C 56.3; H 4.7; N 32.8. C12H12N6O.
Calculated, %: C 56.24; H 4.72; N 32.79.
N1-Dimethylaminocarbonyl-N-(6-tert-butyl-3-
hydrazino-4,5-dihydro-1,2,4-triazin-5-one) (IV). In
20 ml of DMF was dissolved 0.91 g (5 mmol) of 4,5-di-
hydro-1,2,4-triazin-5-one ІІ and at stirring was added
1.05 g (7 mmol) of N,N-dimethylcarbamoyl bromide. The
mixture was stirred at 45–50°C over 3.5–4 h. On cooling
the precipitate was filtered off and recrystallized from
ethanol. Yield 0.85 g (67%), yellow crystals, t.decomp.
268–269°C (EtOH). IR spectrum, ν, cm–1: 3158, 3060,
2920, 1710, 1680, 1610, 1580, 1565, 1515, 1435, 1328,
1310, 1263, 1250, 1156, 1015, 995, 892, 816, 788, 700,
684, 564. 1H NMR spectrum (DMSO-d6), δ, ppm: 1.29 s
(9H, t-Bu), 1.52 s (6H, Me), 13.2 s (1H, NH). Mass spec-
trum, m/z: 255 [M]+, 205, 192, 186, 185, 171, 170, 143,
138, 115, 111, 110, 103, 86, 84, 83, 82, 69, 68, 67, 64, 59,
57, 56, 55, 53, 43, 42, 41. Found, %: C 47.2; H 7.1; N 33.1.
C10H18N6O2. Calculated, %: C 47.24; H 7.13; N 33.05.
IR spectra were recorded on a spectrophotometer
1
UR-10 from pellets with KBr. H NMR spectra were
registered on a spectrometer Varian Mercury VX-200
(200 MHz) in DMSO-d6, internal reference HMDS. The
mass spectrum was taken on a mass spectrometer MS-
1302. The purity of compounds obtained was checked
by TLC on Silufol UV-254 plates, eluent ethyl acetate–
chloroform–acetone, 1 : 3 : 1.
REFERENCES
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tekhn. VINITI, Ser. Org. Khim., 1990, vol. 22, p. 267.
2. Mironovich, L.M., Zh. Org. Khim., 2002, vol. 38, p. 1743.
3. Kalfus, K., Coll. Czech. Chem. Commun., 1968, vol. 33,
p. 2513.
4. Heinisch, L., J. Prakt. Chem., 1974, vol. 316, p. 667.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010