Mendeleev Commun., 2017, 27, 285–286
O2N
K+
H(1)
O(1)
C(3)
H(1)
O(1)
O
N(2)
F(2)
C(2)
H(9)
N
N
X
O(2)
KNO2
HCl
2
C(9)
NH
NH
NH2
O(2)
F(2)
C(2)
N(2)
R
R
H(9)
N(3)
HCl
N(1)
F(1A)
X
C(3)
N(3)
N2
C(9)
C(8)
N(6)
O(3)
N(7)
C(5)
N(4)
F(3)
3a–h
4a–h
F(3)
N(1)
N(4)
OH
F(1)
F(2A)
O(1)
C(5)
N(6)
H(6)
O(1S)
Yield
of 5 (%)
C(8)
N(7)
NO2
F(3A)
N
X
R
X
N
H(6)
R
H(1SB)
H(1SA)
a
H
Me
SMe
CO2Et
Ph
CF3
2-thienyl
H
N
N
N
N
N
N
N
40
41
45
11
18
25
9
N
N
b
c
d
e
f
H
Figure 1 Molecular structure of 5f.
5a–h
azole to a solution of nitroacetaldehyde formed after the addition
of acid to the latter. In both cases the yields are close. The synthesis
of azolotriazines 5 with a previously prepared salt 2 has no
synthetic advantage over that with the nitroacetaldehyde potas-
sium salt solution prepared in situ. Moreover, 1-morpholino-2-nitro-
ethene 1 does not require special storage conditions unlike salt 2.
In conclusion, we have developed a new effective and simple
method for the synthesis of nitroacetaldehyde potassium salt and
obtained new azolo[5,1-c][1,2,4]triazines using this reactant.
g
h
CCO2Et
49
Scheme 2
of the triazine ring and the associated doublet of the OH group
at d 7.5–8.5 ppm, along with the signals of substituents R.
Characteristic signals in the 13C NMR spectra are observed at
d 70–74 ppm (C4) and 130–150 ppm (C3, C7 and C8a).
Azo coupling was performed in acidic medium to avoid the
possible side reaction of diazoazoles 4 with morpholine. There
are several ways of carrying out the reaction: addition of the solu-
tion of nitroacetaldehyde potassium salt to the diazoazole mixture
containing excess acid to form morpholine salt or addition of diazo-
The work was supported by the Russian Science Foundation
(grant nos. 16-13-00008 and 14-13-01301).
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2017.05.023.
§
3-Nitro-1,4-dihydro-1,2,4-triazolo[5,1-c][1,2,4]triazin-4-ol monohydrate
5a. Method 1. A solution of KNO2 (0.936 g, 0.011 mol) in water (3 ml)
was added portionwise to a mixture of 3-amino-1,2,4-triazole 3a (0.84 g,
0.01 mol), water (3 ml), acetonitrile (2 ml) and 12 m HCl (4.6 ml, 0.055
mol) at –7 to –10°C. The mixture was kept at this temperature for 10 min
and the freshly prepared solution A (1.5 equiv.) was added. The mixture
was kept at room temperature for 1 h. The precipitate was filtered, washed
with cold acetonitrile–water (1:1) and dried in air. The product was purified
by chromatography on silica gel (eluent, ethyl acetate), the most mobile
fraction was separated, the solvent was removed to dryness. The residue
was recrystallized from water, filtered and dried. Yield 0.808 g (32%).
Method 2. A solution of KNO2 (0.936 g, 0.011 mol) in water (3 ml)
was added portionwise to a mixture of 3-amino-1,2,4-triazole 3a (0.84 g,
0.01 mol), water (3 ml), acetonitrile (2 ml) and 12 m HCl (3.3 ml, 0.04 mol)
at –7 to –10°C. The reaction mixture was kept at this temperature for
10 min and nitroacetalehyde potassium salt 2 (1.905 g, 0.015 mol) in
water (10 ml) was added. The mixture was kept at room temperature for
1 h. Isolation and purification were carried out like in method 1. Yield
0.812 g (40%), pale yellow powder, mp 232–235 (decomp.). 1H NMR, d:
6.99 (d, 1H, CH, J 7.9 Hz), 8.03 (s, 1H, CH), 8.15 (d, 1H, OH, J 7.9 Hz),
13.38 (br.s., 1H, NH). 13C NMR, d: 72.50 (C4), 142.29 (C3), 146.03 (C8a),
151.44 (C7). DEPT-135 13C NMR, d: 72.50 (C4), 151.44 (C7). IR (n/cm–1):
566, 657, 699, 751, 847, 904, 986, 1071, 1166, 1201, 1250, 1276, 1326,
1531, 1571, 1634, 2737, 2845, 3091, 3361, 3527. Found (%): C, 23.66;
H, 2.89; N, 41.45. Calc. for C4H4N6O3·H2O (%): C, 23.77; H, 2.99; N, 41.58.
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¶
Crystal data for 5f. C5H5N6F3O4 (M = 270.13), monoclinic, space
group P21/n, a = 11.430(12), b = 5.630(7) and c = 15.64(2) Å, b =
= 103.10(10)°, V = 980(2) Å3, m(MoKa) = 1.714 mm–1. Analysis was
performed at 295(2) K on an Xcalibur 3 diffractometer by standard
procedure (graphite monochromated MoKa radiation, w-scanning). On
the angles 4.36 < q < 65.23° total of 7324 reflections were measured,
1660 unique reflections (Rint = 0.0390), 1507 reflections with I > 2s(I).
The structure was solved and refined using the SHELXTL program
package. The structure was defined by direct statistical methods and refined
by full-matrix anisotropic approximation for F2 for all non-hydrogen
atoms with ShelXL program. The hydrogen atoms were localized by
direct method and refined in the isotropic approximation. GOOF = 1.007,
S = 1.038; final R values: R1 = 0.0443, wR2 = 0.1361 [I > 2s(I)]; R1 =
= 0.0476, wR2 = 0.1396 (all data). Residual electronic density max/min
was 0.312/–0.247 eÅ–3.
CCDC 1529899 contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cambridge
Received: 23rd September 2016; Com. 16/5054
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