The corresponding potassium dithiocarbamate 9 was synthesized as a compound with potential
fungicidal activity.
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In the H NMR spectra of the synthesized compounds 6-9 signals were displayed corresponding to the
protons of the 8-substituent, in place of the signal of the NH group proton in compound 5 (Table 2).
EXPERIMENTAL
1
The H NMR spectra were taken on a Mercury-300 (300 MHz) NMR spectrometer in DMSO-d6,
internal standard was TMS. TLC was carried out on Silufol UV-254 plates in the system acetone–hexane, 1:2.
(2-Dimethylamino-6-methoxycarbonylmethylamino-sym-triazin-4-yl)trimethylammonium Chloride
(1) was obtained by the procedure described in [2]. Yield was 92%; mp 155-156°C. Found, %: Cl 11.37;
N 27.80. C11H21ClN6O2. Calculated, %: Cl 11.65; N 27.58.
6-(2-Chloroethoxy)-2-dimethylamino-4-methoxycarbonylmethylamino-sym-triazine (2). Ethylene
chlorohydrin (3.2 g, 40 mmol) was added to a suspension of 84% KOH (powder) (0.7 g, 10 mmol) in dry CHCl3
(10 ml) at 0°C, then compound 1 (3.0 g, 10 mmol) was added in portions. The reaction mixture was stirred for
30 min at 0°C, then for 4 h at 20°C. The mixture was filtered, the filtrate evaporated, the residue was treated
with water (10 ml), and compound 2 was filtered off.
(2-Dimethylamino-4-oxo-6,7-dihydro-4H-imidazo[1,2-a]-1,3,5-triazin-8-yl)acetic Acid Methyl
Ester (3). A. A solution of compound 2 (1.45 g, 5 mmol) in absolute benzene (15 ml) was boiled for 10 h. The
benzene was decanted, and the glassy mass was triturated sequentially with hexane and with petroleum ether,
filtered, and rapidly transferred to a desiccator over H2SO4. Compound 3 hydrochloride (1.0 g, 69%) was
obtained of decomposition point 96-97°C. A suspension of the latter in dry acetone (10 ml) was then neutralized
with K2CO3 powder (0.24 g, 1.7 mmol). After 3 h the KCl was filtered off, and compound 3 was isolated (0.6 g,
69%) from the filtrate as a readily water-soluble viscous liquid.
B. Compound 5 (0.9 g, 5 mmol) was added to a suspension of 84% KOH powder (0.35 g, 5 mmol) in
DMF (10 ml) and the mixture was stirred for 2 h at 20°C. Methyl bromoacetate (0.8 g, 5 mmol) was added and
the mixture heated for 6 h at 75-80°C, cooled, the KBr filtered off, and DMF was distilled from the filtrate at
68-70°C (40 mm Hg), the residue was triturated with hexane, and the latter decanted. Compound 3 (1.1 g, 88%)
was obtained in the residue as a viscous liquid, readily soluble in water.
(2-Dimethylamino-4-oxo-6,7-dihydro-4H-imidazo[1,2-a]-1,3,5-triazin-8-yl)acetic Acid Hydrazide
(4). Hydrazine hydrate (63%, 2 ml) was added to a solution of compound 3 (0.76 g, 3 mmol) in water (2 ml) and
the mixture maintained at 20°C during 3 h. Compound 4 was filtered off and dried in the air.
2-Dimethylamino-7,8-dihydro-6H-imidazo[1,2-a]-1,3,5-triazin-4-one (5) was obtained by the method
1
described in [6]. H NMR spectrum, δ, ppm: 3.08 [6H, s, N(CH3)2]; 3.57-3.95 (4H, m, NCH2CH2N); 8.10 (1H,
br. s, NH).
(2-Dimethylamino-4-oxo-6,7-dihydro-4H-imidazo[1,2-a]-1,3,5-triazin-8-yl)carboxylic Acid Phenyl-
amide (6a). A mixture of compound 1 (1.8 g, 10 mmol) and freshly distilled phenyl isocyanate (1.19 g,
10 mmol) in absolute toluene (10 ml) was boiled in the presence of catalytic quantities of pyridine for 5 h. The
precipitate of compound 6a was filtered off and washed on the filter with benzene (10 ml).
Compounds 6b-d were obtained analogously.
8-Acetyl-2-dimethylamino-7,8-dihydro-6H-imidazo[1,2-a]-1,3,5-triazin-4-one (7). A mixture of
compound 5 (1.8 g, 10 mmol) in acetic anhydride (10 ml) was boiled for 8 h. The solution was evaporated, the
solid triturated under hexane, then boiled with petroleum ether, and solid compound 7, which dissolved well in
water, was filtered off.
2-Dimethylamino-8-tosyl-7,8-dihydro-6H-imidazo[1,2-a]-1,3,5-triazin-4-one (8a). A suspension of
compound 5 (1.8 g, 10 mmol) and 84% KOH powder (0.7 g, 10 mmol) in DMF (10 ml) was stirred for 2 h at
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Dovlatyan
