TRANSFORMATION OF 3,4-BIS(FORMYLAMINO)PYRIDINE
1527
Scheme 2.
[4,5-c]pyridine 2-oxide (IV) and 2.5 g of iron in 35 ml
of glacial acetic acid was heated for 3–4 h. The mix-
ture was cooled and filtered, the filtrate was evapo-
rated to dryness, the residue was treated with 25%
aqueous ammonia and the solution was evaporated to
dryness. The residue was extracted with ethanol, and
the solvent was distilled off from the extract. Yield
0.5 g (67%), mp >325°C (decomp.) [9]. IR spectrum,
ν, cm–1: 1690, 1650, 1625. 1H NMR spectrum, δ, ppm:
6.83 d (1H, 7-H, J = 6.0 Hz), 7.35 br.s (2H, NH2),
7.68 d (1H, 6-H, J = 6.0 Hz), 12.05 s (1H, 1-H).
Found, %: C 44.23; H 3.71; N 51.60. C5H5N5. Calcu-
lated, %: C 44.44; H 3.75; N 51.73.
·
H
N
N
N
N
O
N
O
·
–NO2
N
N
N
NO2
m/z 181 (64%)
m/z 135 (100%)
m/z 118 (24%)
·
–OH
were measured on a Specord 75IR spectrophotometer
from samples pelleted with KBr. The mass spectrum
was obtained on a Varian 311-A mass spectrometer.
The purity of the products was checked by TLC on
Silufol UV-254 plates using chloroform–ethanol as
eluent (development with UV light or iodine vapor).
REFERENCES
4-Nitro-1,2,3-triazolo[4,5-c]pyridine 2-oxide
(IV). 3,4-Bis(formylamino)pyridine (III), 1.65 g
(10 mmol), was dissolved in 15 ml of cold concen-
trated sulfuric acid, the solution was cooled to 0–5°C,
2 ml (48 mmol) of concentrated nitric acid (d = 1.52)
was added in portions under stirring, and the mixture
was stirred for 1 h at 0–5°C. The mixture was then
heated to 50–60°C, kept for 2 h at that temperature,
cooled, and poured onto ice. The light yellow precip-
itate was filtered off, washed with a small amount of
ice water, dried, and recrystallized from dimethyl
sulfoxide. Yield 1.0 g (53%), mp >225°C (decomposes
with explosion). IR spectrum, ν, cm–1: 1310 (N→O),
1. Yutilov, Yu.M. and Svertilova, I.A., Khim. Geterotsikl.
Soedin., 1973, p. 138.
2. Yutilov, Yu.M. and Svertilova, I.A., Khim. Geterotsikl.
Soedin., 1986, p. 97.
3. Yutilov, Yu.M. and Svertilova, I.A., Khim. Geterotsikl.
Soedin., 1994, p. 1076.
4. EP Patent Appl. no. 260613, 1988; Chem. Abstr., 1988,
vol. 109, no. 73438c.
5. US Patent no. 4804658, 1989; Ref. Zh., Khim., 1989,
no. 23O107P.
6. Rusinov, V.L. and Chupakhin, O.N., Nitroaziny (Nitro
Azines), Novosibirsk: Nauka, 1991, p. 10.
7. Terent’ev, P.B. and Stankyavichus, A.P., Mass spektro-
metricheskii analiz biologicheski aktivnykh azotistykh
osnovanii (Mass Spectrometric Analysis of Biologically
Active Nitrogenous Bases), Vil’nyus: Mokslas, 1987,
p. 140.
1
1365 (NO2, sym.), 1540 (NO2, asym.). H NMR spec-
trum, δ, ppm: 7.72 d (1H, 7-H, J = 6.0 Hz), 8.04 d (1H,
6-H, J = 6.0 Hz). Mass spectrum, m/z (Irel, %): 181
(64) [M]+, 135 (100), 118 (24). Found, %: C 33.05;
H 1.62; N 38.81. C5H3N5O3. Calculated, %: C 33.16;
H 1.67; N 38.67.
8. Hertog, H.J. and Overhoff, J., Recl. Trav. Chim. Pays–
Bas, 1950, vol. 69, p. 468.
4-Amino-1,2,3-triazolo[4,5-c]pyridine (V). A mix-
ture of 1.0 g (5.5 mmol) of 4-nitro-1,2,3-triazolo-
9. Temple, C., Smith, B.H., and Montogomery, J.A., J. Org.
Chem., 1972, vol. 37, p. 3601.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 10 2004