1
016
KOBELEV et al.
δ , ppm: 115.5, 116.2, 123.0, 124.7, 125.4, 140.4
(2H, CH ), 6.51 br.s (2H, NH ), 7.07 m (2H, Harom),
8.00 m (2H, Harom), 13.98 br.s (1H, N H). C NMR
C
2
2
3
2
2
13
(
Carom), 150.6 (C ), 153.7 (C ). Found, %: C 58.92;
H 3.11; N 8.57. C H NO . Calculated, %: C 58.90;
spectrum, δ , ppm: 14.4 (Me), 40.0 (CH ), 63.7
8
5
3
C
2
6
H 3.09; N 8.59.
Compound 2b was synthesized in a similar way.
-Chloro-2H-1,4-benzoxazine-2,3(4H)-dione
2b). Yield 0.150 g (76%), colorless crystals, mp 308–
(OCH
48.4 (C ), 162.9 (C ), 168.8 (C ), 193.4 (ArCO).
Found, %: C 50.99; H 4.63; N 18.30. C H N O S.
2
), 114.4 (2C), 128.7, 130.7 (2C), 144.2 (C ),
5
4'
3
1
1
3
14
4
3
6
Calculated, %: C 50.97; H 4.61; N 18.29.
(
3
3
–
1
4-Amino-6-[2-(4-chlorophenyl)-2-oxoethyl]-3-
sulfanylidene-3,4-dihydro-1,2,4-triazin-5(2H)-one
10°C (decomp., from dioxane). IR spectrum, ν, cm :
1
086 br (NH), 1781, 1714 (C=O). H NMR spectrum,
(
3c). Yield 0.214 g (72%, a), 0.220 g (74%, b); yellow
δ, ppm: 7.08 m (1H, Harom), 7.14 m (1H, Harom), 7.28 m
1
3
powder, mp 220–222°C (decomp.). IR spectrum, ν,
(
1H, Harom), 11.90 br.s (1H, NH). C NMR spectrum,
–
1
5
cm : 3200 br (N–H), 1679 (C=S, C =O), 1667
δ , ppm: 114.8, 117.8, 122.5, 126.9, 128.3, 139.5
C
1
3
2
(ArC=O). H NMR spectrum, δ, ppm: 4.40 s (2H,
(
Carom), 150.5 (C ), 153.2 (C ). Found, %: C 46.62;
CH ), 6.51 br.s (2H, NH ), 7.64 m (2H, Harom), 8.05 m
2
2
H 2.05; N 7.07. C H ClNO . Calculated, %: C 46.63;
8
4
3
2
13
(
2H, Harom), 14.01 br.s (1H, N H). C NMR spectrum,
H 2.04; N 7.09.
δ , ppm: 40.5 (CH ), 128.9 (2C), 130.2 (2C), 134.6,
C
2
4
-Amino-6-(2-oxo-2-phenylethyl)-3-sulfanyli-
6
5
3
1
38.7 (Carom), 143.7 (C ), 148.3 (C ), 168.8 (C ), 194.3
ArCO). Found, %: C 44.55; H 3.09; N 18.86.
C H ClN O S. Calculated, %: C 44.53; H 3.06;
dene-3,4-dihydro-1,2,4-triazin-5(2H)-one (3a).
a. Thiocarbonohydrazide, 0.106 g (1.0 mmol), was
added to a solution of 0.319 g (1.0 mmol) of 1a in
(
1
1
9
4
2
N 18.88.
-Amino-6-[2-(4-bromophenyl)-2-oxoethyl]-
-sulfanylidene-3,4-dihydro-1,2,4-triazin-5(2H)-one
3d). Yield 0.249 g (73%, a), 0.252 g (74%, b); yellow
powder, mp 198–200°C (decomp.). IR spectrum, ν,
1
5 mL of anhydrous dioxane, and the mixture was
4
refluxed for 1–3 min until the violet color typical of 1a
disappeared. The mixture was cooled and partly
evaporated until a solid began to precipitate, and the
precipitate of 3a was filtered off. Yield 0.191 g (73%),
yellow powder, mp 178–180°C (decomp., from EtOH).
3
(
–
1
5
cm : 3197 br (N–H), 1679 (C=S, C =O), 1661
(
1
ArC=O). H NMR spectrum, δ, ppm: 4.39 s (2H,
b. A solution of 0.106 g (1.0 mmol) of thiocarbono-
hydrazide was added to a solution of 0.206 g
CH ), 6.51 br.s (2H, NH ), 7.79 m (2H, Harom), 7.97 m
2
2
2
13
(
2H, Harom), 14.01 br.s (1H, N H). C NMR spectrum,
(
1.0 mmol) of methyl 4-phenyl-2,4-dioxobutanoate
δ , ppm: 40.4 (CH ), 127.9, 130.3 (2C), 131.9 (2C),
C
2
6
5
3
(4a) in 15 mL of ethanol. The mixture was refluxed for
1
34.6 (Carom), 143.7 (C ), 148.3 (C ), 168.8 (C ), 194.5
ArCO). Found, %: C 38.73; H 2.69; N 16.46.
C H BrN O S. Calculated, %: C 38.72; H 2.66;
1
.5 h and cooled, and the precipitate was filtered off.
(
Yield 0.197 g (75%), mp 178–180°C (decomp., from
1
1
9
4
2
–
1
EtOH). IR spectrum, ν, cm : 3196 br (N–H), 1698
N 16.42.
-Amino-6-[2-(4-methoxyphenyl)-2-oxoethyl]-
-sulfanylidene-3,4-dihydro-1,2,4-triazin-5(2H)-one
3e). Yield 0.208 g (71%, a), 0.216 g (74%, b); yellow
powder, mp 187–189°C (decomp.). IR spectrum, ν,
5
1
(
C=S, C =O), 1677 (PhC=O). H NMR spectrum, δ,
4
ppm: 4.41 s (2H, CH ), 6.52 br.s (2H, NH ), 7.58 m
2
2
3
(
(
1
4
2H, Harom), 7.70 m (1H, Harom), 8.04 m (2H, Harom),
2
13
4.01 br.s (1H, N H). C NMR spectrum, δ , ppm:
C
0.4 (CH ), 128.3 (2C), 128.8 (2C), 133.7, 135.9
–1
5
2
cm : 3217 br (N–H), 1661 (C=S, C =O), 1650
(
6
5
3
(
Carom), 143.9 (C ), 148.4 (C ), 168.3 (C ), 195.2
1
ArC=O). H NMR spectrum, δ, ppm: 3.87 (3H,
(
PhCO). Found, %: C 50.39; H 3.87; N 21.34.
OCH ), 4.34 s (2H, CH ), 6.51 br.s (2H, NH ), 7.08 m
3
2
2
C H N O S. Calculated, %: C 50.37; H 3.84; N 21.36.
2
11
10
4
2
(
2H, Harom), 8.01 m (2H, Harom), 13.98 br.s (1H, N H).
1
3
Compounds 3b–3g were synthesized in a similar
way.
C NMR spectrum, δ
(OCH ), 114.0 (2C), 128.9, 130.7 (2C), 144.2 (C ),
48.4 (C ), 163.6 (C ), 168.8 (C ), 194.5 (ArCO).
Found, %: C 49.33; H 4.17; N 19.16. C H N O S.
, ppm: 40.1 (CH ), 55.6
C 2
6
3
5
4′
3
1
4
-Amino-6-[2-(4-ethoxyphenyl)-2-oxoethyl]-
1
2
12
4
3
3
-sulfanylidene-3,4-dihydro-1,2,4-triazin-5(2H)-one
3b). Yield 0.229 g (75%, a), 0.236 g (77%, b); yellow
powder, mp 179–181°C (decomp., from EtOH). IR
Calculated, %: C 49.31; H 4.14; N 19.17.
(
4-Amino-6-[2-(4-methylphenyl)-2-oxoethyl]-
3-sulfanylidene-3,4-dihydro-1,2,4-triazin-5(2H)-one
(3f). Yield 0.169 g (61%, a), 0.171 g (62%, b); yellow
powder, mp 208–210°C (decomp.). IR spectrum, ν,
–
1
5
spectrum, ν, cm : 3226 br (N–H), 1665 (C=S, C =O),
1
1
648 (ArC=O). H NMR spectrum, δ, ppm: 1.37 t (3H,
Me, J = 7.0 Hz), 4.16 q (2H, OCH , J = 7.0 Hz), 4.33 s
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 7 2019