1414
EFIMOVA et al.
from 0.37 g of 1-bromo-1-nitro-2-(4-nitrophenyl)ethene
V and 0.16 g of 1-amino-2-nitroguanidine I. Com-
pound XI was isolated as a diastereomers mixture (a:b =
1:1). Yield 0.48 g (51%), mp 120–122°C (isopro-
panol). Found, %: C 34.92; H 3.66; N 31.68.
C9H10N7O6Br. Calculated, %: C 34.50; H 3.51; N
31.30.
nitrobenzaldehyde and 0.42 g of 1-amino-2-nitro-
guanidine I yielded 0.86 g (95%) of compound XIV,
mp 240–243°C (isopropanol–water, 2:1). For two
samples the melting point depression was not observed.
N-(2-Nitroguanidino-N-(4-chlorophenylmethyl-
idene)amine (XV) was obtained similarly by the a
method from 0.95 g of XII. Yield 0.4 g (65%), mp
210–211°C (isopropanol–water, 2:1). Found N, %:
29.18. C8H8N5O2Cl. Calculated N, %: 29.04.
1-Bromo-1-nitro-2-(2-nitroguanidinoamino)-2-
(4-chlorohenyl)ethane (XI) was obtained similarly
from 0.4 g of 1-bromo-1-nitro-2-(4-chlorophenyl)
ethene VI and 0.18 g of 1-amino-2-nitroguanidine I.
Compound XII was isolated as a diastereomers
mixture (a:b = 3:2). Yield 0.56 g (62%), mp 122–125°C
(isopropanol). Found, %: C 35.98; H 3.64; N 28.70.
C9H10N6O4ClBr. Calculated, %: C 35.76; H 4.12; N
27.81.
The synthesis by the c method from 0.54 g of p-
chlorobenzaldehyde and 0.42 g of 1-amino-2-nitro-
guanidine I yielded 0.56 g (93%) of compound XV,
mp 210–212°C (isopropanol–water, 2:1). For two
samples the melting point depression was not observed.
N-(4-Bromophenylmethylidene)-N-(2-nitroguan-
idino)amine (XVI). To a hot solution of 0.3 g of 1-
bromo-2-(4-bromophenyl)-1-nitroethene VII in 15 ml
of isopropanol was added a solution of 0.115 g of 1-
amino-2-nitroguanidine I in 10 ml of water. The
mixture was boiled for 5 h and cooled to 18–20°C. The
crystalline precipitate was filtered off, washed with
alcohol, ether, and dried in air. Yield 0.02 g (71%), mp
219–220°C (isopropanol–water, 2:1). Found N, %:
24.31. C8H8N5O2Br. Calculated N, %: 24.47.
N-Benzylidene-N-(2-nitroguanidino)amine (XIII).
a. To a solution of 0.25 g of 1-bromo-1-nitro-2-(2-
nitroguanidinoamino)-2-phenylethane X in 25 ml of
isopropanol was added 0.1 ml of triethylamine at 70°C.
The mixture was boiled for 10 min, and then poured
into the cold water. The crystalline precipitate was
filtered off and washed with water. Yield 0.03 g (21%)
mp 182–185°C (isopropanol–water, 2:1) (mp 188°C
[23]). Found, %: C 47.05; H 4.50; N 34.17. C8H9N5O2.
Calculated, %: C 46.37; H 4.34; N 33.81.
REFERENCES
b. To a solution of 0.15 g of 1-bromo-1-nitro-2-(2-
nitroguanidinoamino)-2-phenylethane X in 25 ml of
isopropanol was added a solution of 0.062 g of
potassium acetate in 2 ml of water at 70°C. The
mixture was heated at 80°C for 10 min and poured into
the crushed ice. The crystalline precipitate was filtered
off. Yield 0.03 g (37%), mp 181–183°C (isopropanol–
water, 2:1).
1. Zhaohai, Q., Pat. 2216324 А1 (2010), China.
2. Mashkovskii, M.D., Lekarstvennye sredstva (Drugs),
Moscow: RIA Novaya Volna, 2007.
3. Granik, V.G., Osnovy meditsinskoi khimii (Funda-
mentals of Medicinal Chemistry), Moscow: Vuzovskaya
Kniga, 2001, p. 291.
4. Granik, V.G. Lekarstva (farmakologicheskii, biolo-
gicheskii i khimicheskii aspekty) (Drugs: Pharma-
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Vuzovskaya Kniga, 2006, p. 209.
5. McKay, A.F., Chem. Rev., 1952, no. 51, p. 301.
6. Metelkina, E.L. and Novikova, T.A., Zh. Org. Khim.,
1999, vol. 35, no. 11, p. 1619.
7. Henry, R.A., J. Am. Chem. Soc., 1950, vol. 72, no. 11,
c. To a solution of 0.265 g of benzaldehyde in
10 ml of ethanol was added a solution of 0.3 g of 1-
amino-2-nitroguanidine I in 10 ml of water. The
mixture was heated at 80°C for 5 min and cooled. The
crystalline precipitate was filtered off. Yield 0.5 g
(95%), mp 180–183°C (isopropanol–water, 2:1). For
all samples the melting point depression was not
observed.
p. 5343.
8. Chipen, G.I., Grinshtein, R.P., and Preiman, V.Ya., Zh.
Obshch. Khim., 1962, vol. 32, no. 2, p. 454.
9. McKay, A.F. and Milks, J.E., J. Am. Chem. Soc., 1950,
vol. 72, no. 4, p. 1616.
10. USA Patent no. 2865923, 1958, С. А. 1957–1961,
N-(2-Nitroguanidine)-N-(4-nitrophenylmethyl-
idene)amine (XIV) was obtained similarly by the a
method from 0.98 g of XI. Yield 0.49 g (79%), mp
240–242°C (isopropanol–water, 2:1). Found N, %:
32.57. C8H8N6O4. Calculated N, %: 33.33.
vols. 51–55, p. 141.
11. Worrall, D.E., J. Am. Chem. Soc., 1927, vol. 48, no. 6,
The synthesis by the c method from 0.54 g of p-
p. 1604.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 8 2012