NOSOVA et al.
1548
3
1H NMR spectrum, δ, ppm: 7.16 d.d.d (5'-H, J = 8.0,
trum, m/z (Irel, %): 374 [M]+ (42), 185 (13), 184 (100),
162 (11), 77 (10). Found, %: C 54.51; H 2.38; N 14.96.
C17H9F3N4OS. Calculated, %: C 54.55; H 2.41;
N 14.97.
5.0, 4J = 0.5 Hz), 7.29 d.d (3'-H, 3J = 8.0, 4J = 0.5 Hz),
3
4
7.81 t.d (4'-H, J = 8.0, J = 1.5 Hz), 7.97 d.d.d (5-H,
3J = 9.8, 4J = 7.5, 5J = 2.3 Hz), 8.41 d.d (6'-H, 3J = 5.0,
4J = 1.5 Hz), 12.2 br.s (1H, NH). F NMR spectrum,
19
b. A solution of 0.3 g (0.9 mmol) of thiourea IIIa in
3 ml of DMSO was heated for 3 min at the boiling
point, and the precipitate of IVa was filtered off and
recrystallized from DMSO. Yield 0.25 g (90%).
δF, ppm: 10.12 m (1F), 26.20 m (1F), 27.37 m (1F).
Mass spectrum, m/z (Irel, %): 309 [M]+ (30), 308 (19),
190 (19), 162 (23), 119 (100), 78 (35). Found, %:
C 50.53; H 1.97; N 13.55. C13H6F3N3OS. Calculated,
%: C 50.49; H 1.94; N 13.59.
Compounds IVb–IVh were synthesized in a similar
way. Yield of IVc 87%, yield of IVd 88%.
Compounds IVc, IVd, IVi, and IVj were syn-
thesized in a similar way. In the synthesis of IVi and
IVj, the reaction mixture was heated under reflux for
6 h. Compounds IVd and IVj were recrystallized from
DMSO.
5,6,7,8-Tetrafluoro-2-(pyridin-2-ylamino)-1,3-
benzothiazin-4-one (IVb). Yield 88%, mp 220–
1
222°C. H NMR spectrum, δ, ppm: 7.14 d.d.d (5'-H,
3J = 7.8, 5.0, 4J = 0.8 Hz), 7.29 d.d (3'-H, 3J = 7.8, 4J =
3
0.8 Hz), 7.79 t.d (4'-H, J = 7.8, 4J = 1.5 Hz), 8.38 d.d
3
4
6,7,8-Trifluoro-2-(6-methylpyridin-2-ylamino)-
(6'-H, J = 5.0, J = 1.5 Hz), 12.2 br.s (1H, NH).
19F NMR spectrum, δF, ppm: 5.52 m (1F), 13.11 m
(1F), 20.97 m (1F), 25.40 m (1F). Mass spectrum, m/z
(Irel, %): 327 [M]+ (28), 326 (15), 208 (21), 180 (22),
120 (12), 119 (100), 78 (56), 51 (12). Found, %:
C 47.73; H 1.55; N 12.80. C13H5F4N3OS. Calculated,
%: C 47.71; H 1.53; N 12.84.
1,3-benzothiazin-4-one (IVc). Yield 70%, mp 216–
1
218°C. H NMR spectrum, δ, ppm: 2.42 s (3H, CH3),
3
3
7.00 d (5'-H, J = 7.8 Hz), 7.10 d (3'-H, J = 4.6 Hz),
3
3
7.69 d.d (4'-H, J = 7.8, 4.6 Hz), 7.97 d.d.d (5-H, J =
4
5
10.0, J = 7.6, J = 2.1 Hz), 11.7 br.s (1H, NH). Mass
spectrum, m/z (Irel, %): 323 [M]+ (21), 322 (14), 190
(9), 162 (13), 134 (9), 133 (100), 92 (24), 91 (10), 69
(11), 65 (14). Found, %: C 52.04; H 2.52; N 12.97.
C14H8F3N3OS. Calculated, %: C 52.01; H 2.48;
N 13.00.
6,7,8-Trifluoro-2-(pyrimidin-2-ylamino)-1,3-
benzothiazin-4-one (IVe). Yield 89%, mp 262–264°C.
3
1H NMR spectrum, δ, ppm: 7.27 t (5'-H, J = 4.9 Hz),
8.02 d.d.d (5-H, 3J = 10.0, 4J = 7.7, 5J = 2.2 Hz), 8.78 d
(4'-H, 6'-H, 3J = 4.9 Hz), 12.5 br.s (1H, NH). 19F NMR
spectrum, δF, ppm: 10.09 m (1F), 27.35 m (1F),
27.92 m (1F). Mass spectrum, m/z (Irel, %): 310 [M]+
(40), 191 (13), 190 (100), 162 (43), 120 (25). Found,
%: C 46.39; H 1.58; N 18.08. C12H5F3N4OS. Calculat-
ed, %: C 46.41; H 1.61; N 18.05.
5,6,7,8-Tetrafluoro-2-(6-methylpyridin-2-yl-
amino)-1,3-benzothiazin-4-one (IVd). Yield 73%,
1
mp 217–219°C. H NMR spectrum, δ, ppm: 2.46 s
(3H, CH3), 6.96 d (5'-H, 3J = 7.7 Hz), 7.17 d (3'-H, 3J =
4.5 Hz), 7.67 d.d (4'-H, 3J = 7.7, 4.5 Hz), 12.1 br.s (1H,
NH). Mass spectrum, m/z (Irel, %): 341 [M]+ (17), 133
(100), 92 (24), 65 (13). Found, %: C 49.31; H 2.08;
N 12.29. C14H7F4N3OS. Calculated, %: C 49.27;
H 2.05; N 12.32.
5,6,7,8-Tetrafluoro-2-(pyrimidin-2-ylamino)-1,3-
benzothiazin-4-one (IVf). Yield 87%, mp 279–281°C.
3
1H NMR spectrum, δ, ppm: 7.25 t (5'-H, J = 5.0 Hz),
3
6,7,8-Trifluoro-2-(5-methyl-1H-pyrazol-3-yl-
amino)-1,3-benzothiazin-4-one (IVi). Yield 66%,
8.75 d (4'-H, 6'-H, J = 5.0 Hz), 12.4 br.s (1H, NH).
19F NMR spectrum, δF, ppm: 6.05 m (1F), 13.78 m
(1F), 21.19 m (1F), 25.52 m (1F). Mass spectrum, m/z
(Irel, %): 328 [M]+ (40), 209 (12), 208 (100), 180 (38),
148 (12), 120 (54). Found, %: C 43.90; H 1.26;
N 17.05. C12H4F4N4OS. Calculated, %: C 43.87;
H 1.23; N 17.06.
1
mp >250°C. H NMR spectrum, δ, ppm: 2.27 s (3H,
CH3), 5.79 s (4'-H), 7.98 d.d.d (5-H, 3J = 9.8, 4J = 6.8,
5J = 2.0 Hz), 12.0 br.s (1H, NH), 12.2 br.s (1H, NH).
Mass spectrum, m/z (Irel, %): 312 [M]+ (45), 191 (13),
190 (13), 162 (15), 122 (100), 121 (11). Found, %:
C 46.13; H 2.22; N 17.99. C12H7F3N4OS. Calculated,
%: C 46.15; H 2.24; N 17.95.
2-(4,6-Dimethylpyrimidin-2-ylamino)-6,7,8-tri-
fluoro-1,3-benzothiazin-4-one (IVg). Yield 85%,
1
mp >250°C. H NMR spectrum, δ, ppm: 2.48 s (3H,
6,7,8-Trifluoro-2-(5-phenyl-1H-pyrazol-3-yl-
amino)-1,3-benzothiazin-4-one (IVj). Yield 66%,
CH3), 2.51 s (3H, CH3), 6.96 s (5'-H), 7.98 d.d.d (5-H,
1
4
5
mp >250°C. H NMR spectrum, δ, ppm: 6.43 s (4'-H),
3J = 9.8, J = 6.8, J = 2.0 Hz), 12.2 br.s (1H, NH).
19F NMR spectrum, δF, ppm: 9.45 m (1F), 25.27 m
(1F), 27.68 m (1F). Mass spectrum, m/z (Irel, %): 338
[M]+ (39), 190 (63), 162 (30), 149 (10), 148 (100), 107
7.32 m (1H, C6H5), 7.42 m (2H, C6H5), 7.72 m (2H,
C6H5), 7.98 d.d.d (5-H, 3J = 9.9, 4J = 7.8, 5J = 2.2 Hz),
11.8 br.s (1H, NH), 13.2 br.s (1H, NH). Mass spec-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 10 2006