FORMATION OF PYRIMIDIN-2-YLCYANAMIDE
1225
Arylguanidines VIII–X. General procedure [4,
5, 7]. To a solution of 0.01 mol of nitroaniline I, II, VII
in 15 ml of anhydrous ethanol at cooling to 0°C was
added dropwise 0.45 ml (0.01 mol) of 65% nitric acid;
yellow dispersion formed. At the end of self-heating
1 ml (0.012 mol) of 50% water solution of cyanamide
was added, and the reaction mixture was boiled for 12 h.
Then again 1 ml (0.012 mol) of 50% water solution of
cyanamide and 0.45 ml (0.01 mol) of 65% nitric acid were
added (pH of the reaction mixture ~3), and the heating
was continued for 6–18 h. The separated precipitate of the
guanidine nitrate was filtered off, washed with the mixture
ethanol–ethyl ether, 1 : 1, and recrystallized from ethanol.
slightly colored crystals, mp 280–282°C. IR spectrum, ν,
cm–1: 3400, 3160, 2950, 1680, 1630, 1580, 1520, 1350.
Mass spectrum, m/z (Irel, %): [M]+ 179.98 (100), [M –
NH2CNH]+ 137.97, 107.96 (34), 91.96 (21), [NH2CNH]+
42.95 (39). Found, %: N 25.44. C7H9ClN4O2. Calculated,
%: N 25.87.
Reaction of derivatives III–VII with cyanamide
and 3-dimethylamino-1-(pyridin-3-yl)-2-propenone
(XI). From the reaction mixture obtained by the above
procedure from anilines III–VII with cyanamide in the
presence of nitric acid the precipitate was filtered off and
added to the solution of 1 equiv of 3-dimethylamino-1-
(3-pyridyl)-2-propen-1-one (XI) in 2-propanol. Into the
mixture a hot solution of 1.2 equiv of NaOH in 2-propanol
was added, and the mixture was boiled for 18–24 h. The
precipitate was filtered off, washed with 2-propanol and
ethyl ether (3 × 50 ml).
N1-Amino(imino)methyl-2-methyl-5-nitroaniline
nitrate (VIII). Yield 92%, slightly colored crystals,
mp 220–224°C (mp 219–226°C from 2-propanol [6]).
IR spectrum, ν, cm–1: 3490, 3360, 3150, 1680, 1580,
1
1515, 1475, 1310. H NMR spectrum (DMSO-d6), δ,
From compounds IV–VI N-[4-(pyridin-3-yl)pyrim-
idin-2-yl]cyanamide (XII) was obtained. Yield 75%,
ppm: 1.30 s (3H, CH3), 3.34 s (1H, NH), 6.57 br.s (3H,
3
NH2, NH), 6.78 d (1H, Harom, J 8.5 Hz), 7.24 d (1H,
slightly colored crystals, mp 232–234°C. IR spectrum,
H
arom, 4J 2.5 Hz), 7.30 d.d (1H, Harom, 3J 8.5, 4J 2.5 Hz).
1
ν, cm–1
: 3380 (NH), 2160 (C≡N), 1445, 1567. H NMR
13C NMR spectrum, δ, ppm: 17.40, 122.30, 122.57,
132.00, 134.30, 143.50, 146.16, 155.87. Mass spectrum,
m/z (Irel, %): [M]+ 194 (100), [M – Me]+ 179 (78), [M –
NO2]+ 147 (43), [M + 1]+ 195 (10), 106, 94, 77. Found,
%: N 27.54. C8H11N5O5. Calculated, %: N 27.24.
spectrum (D2O), δ, ppm: 7.09 d (1H, Harom, 4J 5.3 Hz),
7.47 d.d (1H, Harom, 3J 7.9, 4J 5.0 Hz), 8.25 t (1H, Harom
4J 1.8 Hz), 8.26 d (1H, Harom, 3J 5.3 Hz), 8.53 d.d (1H,
arom, 3J 4.9, 4J 1.5 Hz), 8.93 d (1H, Harom, 4J 1.7 Hz).
,
H
13C NMR spectrum (D2O), δ, ppm: 108.30, 124.35,
125.68, 132.64, 135.96, 147.32, 150.37, 159.32, 163.39,
167.52. Mass spectrum: [M]+ 197. Found, %: N 36.01.
C10H7N5. Calculated, %: N 35.51. M 197.20.
N1-Amino(imino)methyl-4-methyl-3-nitroaniline
nitrate (IX). Yield 91%, slightly colored crystals,
mp 218°C. IR spectrum, ν, cm–1: 3380, 1690–1580,
1
1550, 1345. H NMR spectrum (CDCl3), δ, ppm: 2.50 s
From compound III 4-(pyridin-3-yl)-pyrimidin-2-
ylamine (XIII) was obtained. Yield 70%, slightly colored
crystals, mp 180–182°C. IR spectrum, ν, cm–1: 3540, 3380
(3H, Me), 5.07 br.s (4H, NH, NH2), 7.03 d.d (1H, Harom
,
3J 8.2, 4J 2.2 Hz), 7.19 d (1H, Harom, 3J 8.2 Hz), 7.39 d
(1H, Harom, 4J 2.2 Hz). 13C NMR spectrum, δ, ppm: 19.09,
117.95, 123.03, 128.07, 132.25, 149.07, 149.83, 153.15.
Mass spectrum, m/z (Irel, %): [M]+ 194 (100), [M – Me]
1
(NH). H NMR spectrum (CDCl3), δ, ppm: 5.22 br.s (2H,
NH2), 7.07 d (1H, Harom, 3J 5.4 Hz), 7.41 d.d (1H, Harom
,
3J 7.8, 4J 4.8 Hz), 8.31 d ( 1H, Harom, 3J 7.8 Hz), 8.40 d
+
179 (67), [M – NO2] + 147 (33). Found, %: N 27.64.
3
4
(1H, Harom, J 5.4 Hz), 8.71 d (1H, Harom, J 4.7 Hz),
9.20 s (1H, Harom). 13C NMR spectrum, δ, ppm: 107.61,
123.56, 132.76, 134.41, 148.49, 151.38, 159.20, 162.94,
163.31. Mass spectrum: [M]+ 173.
C8H11N5O5. Calculated, %: N 27.24.
N1-Amino(imino)methyl-4-methyl-3-(4-carboxy-
benzylamino)aniline nitrate (X). Yield 67%, red-violet
light crystals, mp 136–138°C. IR spectrum, ν, cm–1: 3480,
3360, 3150, 1680, 1580, 1475, 1310.Mass spectrum, m/z
(Irel, %): [C6H5CO2]+ 121 (100), [M]+ 298 (90), 135 (60),
107 (25), 89 (25), 77. Found, %: N 18.90. C16H19N5O5.
Calculated, %: N 19.38.
N1-Amino(imino)methyl-4-nitroaniline hydro-
chloride was similarly prepared from 4-nitroaniline us-
ing hydrochloric acid instead of nitric acid. Yield 25%,
By GC-MS analysis of the reaction mixture cyanogua-
nidine A [mass spectrum, m/z (Irel, %): [M]+ 84 (100), 68
(54), 43 (100), C2H4N4] and 2,4,6-triamino-1,3,5-triazine
B [mass spectrum, m/z (Irel, %): [M]+ 126, 85 (20), 68
(12), 43 (50), C3H6N6] were detected.
Comound XIII was also obtained by reduction of
compound XII with hydrazine hydrate in the presence
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011