FLUORINE-CONTAINING HETEROCYCLES: XVI.
73
heated for 1 h under reflux, and cooled, and the precip-
itate was filtered off and recrystallized from DMSO.
Yield 1.6 g (76%), mp 274–276°C. 1H NMR spectrum,
δ, ppm: 7.52 m (4H, Harom), 7.62 m (2H, Harom), 7.81 m
(2H, 6'-H, 6''-H), 8.42 m (2H, Harom), 8.44 m (2H,
anhydrous acetonitrile. The mixture was kept for
30 min at room temperature, heated for 1 h under
reflux, cooled, and evaporated, and the residue was
washed with ethanol and recrystallized from DMSO.
1
Yield 1.37 g (92%), mp 176–178°C. H NMR spec-
H
arom), 8.74 s (1H, 5-H), 13.2 br.s (1H, NH). 19F NMR
trum, δ, ppm: 7.51 m (3H, Harom), 7.67 m (1H, 6'-H),
7.93 m (2H, Harom), 11.0 br.s (1H, NH), 12.0 br.s (1H,
NH), 12.1 br.s (1H, NH). Found, %: C 48.55; H 2.47;
N 11.30. C15H9F4N3O2S. Calculated, %: C 48.52;
H 2.44; N 11.32.
spectrum, δF, ppm: 7.49 m (1F), 8.00 m (1F), 12.13 m
(1F), 12.58 m (1F), 22.98 m (1F), 24.00 m (1F), 24.46
m (1F), 24.71 m (1F). Mass spectrum, m/z (Irel, %):
698 [M]+ (17), 549 (15), 231 (33), 189 (39), 177 (100),
149 (24), 129 (27), 77 (12). Found, %: C 54.98;
H 1.99; N 12.07. C32H14F8N6O2S. Calculated, %:
C 55.02; H 2.02; N 12.03.
Compounds XIb–XId were synthesized in a similar
way.
2,3,4,5-Tetrafluoro-N-[2-(3-nitrobenzoyl)hydra-
zinocarbothioyl]benzamide (XIb). Yield 86%,
2,3,4,5-Tetrafluoro-N-{2-(2,3,4,5-tetrafluoroben-
zoylaminocarbothioyl)-2,3-dihydro[1,2,4]triazolo-
[3,4-b][1,3]benzothiazol-3-ylidene}benzamide (IXa).
A solution of 9 mmol of isothiocyanate I in acetonitrile
(prepared as described above) was added to a suspen-
sion of 0.74 g (4.5 mmol) of 1,3-benzothiazol-2-ylhy-
drazine (VIIIa) in 10 ml of anhydrous acetonitrile. The
mixture was kept for 30 min at room temperature,
heated for 1 h under reflux, and cooled, and the precip-
itate was filtered off and recrystallized from DMSO.
Yield 2.1 g (78%), mp 253–255°C. 1H NMR spectrum,
δ, ppm: 7.50 m (1H, benzothiazole), 7.60 m (1H, ben-
zothiazole), 7.94 m (1H, 6'-H), 8.00 m (1H, benzothia-
zole), 8.19 m (1H, 6''-H), 8.24 m (1H, benzothiazole),
13.8 br.s (1H, NH). 19F NMR spectrum, δ, ppm:
7.78 m (1F), 8.10 m (1F), 12.64 m (1F), 13.09 m (1F),
24.09 m (1F), 24.22 m (1F), 24.72 m (1F), 24.97 m
(1F). Mass spectrum, m/z (Irel, %): 601 [M]+ (15), 451
(35), 177 (100), 149 (20), 134 (10). Found, %:
C 45.96; H 1.19; N 11.61. C23H7F8N5O2S2. Calculated,
%: C 45.92; H 1.16; N 11.65.
1
mp 206–208°C. H NMR spectrum, δ, ppm: 7.56 m
3
(1H, 6'-H), 7.80 t (1H, 5-H, J = 7.9 Hz), 8.36 m
(2H, 4-H, 6-H), 8.81 m (1H, 2-H), 10.6 br.s (1H, NH),
11.0 br.s (1H, NH), 12.5 br.s (1H, NH). Found, %:
C 45.30; H 1.94; N 13.44. C15H8F4N4O4S. Calculated,
%: C 45.27; H 1.92; N 13.46.
2,3,4,5-Tetrafluoro-N-[2-(pyridin-3-ylcarbonyl)-
hydrazinocarbothioyl]benzamide (XIc). Yield 83%,
1
mp 177–179°C. H NMR spectrum, δ, ppm: 7.49 m
(1H, 5-H), 7.67 m (1H, 6'-H), 8.24 m (1H, 6-H),
8.72 m (1H, 4-H), 9.06 m (1H, 2-H), 11.3 br.s (1H,
NH), 12.0 br.s (1H, NH), 12.1 br.s (1H, NH). Found,
%: C 45.20; H 2.18; N 15.03. C14H8F4N4O2S. Cal-
culated, %: C 45.17; H 2.16; N 15.05.
2,3,4,5-Tetrafluoro-N-[2-(pyridin-4-ylcarbonyl)-
hydrazinocarbothioyl]benzamide (XId). Yield 91%,
1
mp 172–174°C. H NMR spectrum, δ, ppm: 7.82 m
(3H, 6'-H, 2-H, 6-H), 8.73 m (2H, 3-H, 5-H), 11.4 br.s
(1H, NH), 12.0 br.s (1H, NH), 12.4 br.s (1H, NH).
Mass spectrum, m/z (Irel, %): 372 (13) [M]+, 177 (87),
149 (29), 106 (100), 78 (55), 51 (25). Found, %:
C 45.16; H 2.14; N 15.08. C14H8F4N4O2S. Calculated,
%: C 45.17; H 2.16; N 15.05.
2,3,4,5-Tetrafluoro-N-{2-(2,3,4,5-tetrafluoroben-
zoylaminocarbothioyl)-2,3-dihydro[1,2,4]triazolo-
[3,4-b]benzimidazol-3-ylidene}benzamide (IXb) was
synthesized in a similar way. Yield 71%, mp 284–
1
286°C. H NMR spectrum, δ, ppm: 7.33 m (2H, benz-
3-Phenyl-4-(2,3,4,5-tetrafluorobenzoyl)-4,5-di-
hydro-1H-1,2,4-triazole-5-thione (XIIa). A solution
of 1.1 g (2.96 mmol) of compound XIa in 2 g of di-
phenyl ether was heated for 3 h under reflux. After
cooling, the precipitate was filtered off and recrys-
tallized from DMSO. Yield 0.89 g (85%), mp 225–
227°C. 1H NMR spectrum, δ, ppm: 7.51 m (3H, Harom),
7.74 m (1H, 6'-H), 7.93 m (2H, Harom), 13.4 br.s (1H,
NH). Mass spectrum, m/z (Irel, %): 353 (25) [M]+, 177
(100), 149 (23), 121 (15). Found, %: C 50.95; H 1.98;
N 11.87. C15H7F4N3OS. Calculated, %: C 50.99;
H 2.00; N 11.89.
imidazole), 7.68 m (2H, benzimidazole), 7.93 m (1H,
6'-H), 8.03 m (1H, 6''-H), 13.1 br.s (1H, NH). Mass
spectrum, m/z (Irel, %): 584 [M]+ (15), 451 (31), 177
(100), 149 (25). Found, %: C 47.22; H 1.33; N 14.41.
C23H8F8N6O2S. Calculated, %: C 47.26; H 1.37;
N 14.38.
N-(2-Benzoylhydrazinocarbothioyl)-2,3,4,5-
tetrafluorobenzamide (XIa). A solution of 8 mmol of
2,3,4,5-tetrafluorobenzoyl isothiocyanate (I) in 10 ml
of anhydrous acetonitrile was added to a solution of
0.54 g (4 mmol) of benzohydrazide (Xa) in 8 ml of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 1 2007