NJC
Paper
736, 644, 595, 582, 519. 1H NMR (CD2Cl2, d), 8.04 (d, J(H,H) = 8.8 77Se NMR (CD2Cl2, d), 679.6 and 606.8 ppm. 19F NMR (CD2Cl2,
Hz, 2H), 7.80 (d, J(H,H) = 9.1 Hz, 2H), 7.41 (d, J(H,H) = 8.8 Hz, d), 85.0 (pentet, 2J(F,F) = 150.7 Hz, 1F), 63.4 (d, 2J(F,F) =
2H), 7.08 (s, 1H), 7.07 (s, 1H), 7.04 (d, J(H,H) = 8.8 Hz, 2H), 6.88 149.7 Hz, 4F) ppm. HRMS (EI+, m/z): found 579.8650 [M]+,
(d, J(H,H) = 9.1 Hz, 2H), 6.76 (d, J(H,H) = 8.8 Hz, 2H), 3.81 (s, 3H), calculated mass for C15H9F5N4O3SSe2: 579.8646.
3.75 (s, 3H). 13C NMR (CD2Cl2, d), 174.0, 172.3, 162.9, 159.4,
4-Nitro-N-[3-(4-(pentafluoro-l6-sulfanyl)phenyl)-4-phenyl-1,3-
152.7, 142.0, 139.2, 131.2, 130.5, 129.4, 126.5, 124.3, 113.8, 109.1, selenazol-2(3H)-ylidene]-benzamide (10a). Yellow solid (0.525 g,
63.1, 55.4, 55.3 ppm. 77Se NMR (CD2Cl2, d), 604.2 ppm. 19F NMR 92%). M.p. 180–181 1C. Selected IR (KBr, cmÀ1): 1695, 1590,
(CD2Cl2, d), 83.5 (pentet, 2J(F,F) = 150.8 Hz, 1F), 62.9 (d, 2J(F,F) = 1401, 1261, 1199, 1093, 1014, 994, 812, 724, 668, 548, 530.
149.9 Hz, 4F) ppm. HRMS (EI+, m/z): found 590.0199 [M]+, 1H NMR (CDCl3, d), 8.33–8.26 (m, 3H), 7.89–7.82 (m, 3H),
calculated mass for C24H19F5N2O3SSe: 590.0202.
7.41 (d, J(H,H) = 8.6 Hz, 2H), 7.37–7.30 (m, 4H), 7.16–7.13
Synthesis of compounds 6 and 7. To a solution of 4-meth- (m, 2H) ppm. 13C NMR (CDCl3, d), 173.7, 172.7, 149.8, 141.6,
oxybenzoyl chloride (0.340 g, 2.0 mmol) in dry acetone (30 cm3) 141.3, 139.9, 131.5, 130.1, 129.2, 129.1, 129.0, 128.7, 126.7,
was added dropwise a solution of KSeCN (0.288 g, 2.0 mmol) in 126.5, 123.4, 111.1 ppm. 77Se NMR (CDCl3, d), 621.8 ppm.
dry acetone (10 cm3) at room temperature. The mixture was 19F NMR (CDCl3, d), 83.1 (pentet, J(F,F) = 152.1 Hz, 1F), 63.1
2
stirred at room temperature for 3 h, then 4-bromoaniline (0.342 g, (d, 2J(F,F) = 150.4 Hz, 4F) ppm. HRMS (CI+, m/z): found 575.9938
2.0 mmol) was added and the suspension was stirred in the dark at [M + H]+, calculated mass for C22H14F5N3O3SSeH: 575.9941.
room temperature for another 18 h. After removing solvent in vacuo,
N-[4-(4-Chlorophenyl)-3-(4-(pentafluoro-l6-sulfanyl)phenyl)-1,3-
the residue was purified by silica gel column chromatography selenazol-2(3H)-ylidene]-4-nitrobenzamide (10b). Yellow solid
(eluted by 1 : 1 hexane/dichloromethane) to give the products 6 (0.565 g, 93%). M.p. 225–226 1C. Selected IR (KBr, cmÀ1): 1695,
and 7. Both were prepared and reported previously.
1575, 1521, 1461, 1402, 1337, 1275, 1196, 1093, 1064, 1013, 922,
Synthesis of compounds 8, 9, 10a–d. To a solution of 4-nitro- 903, 835, 774, 720, 658, 582, 406. 1H NMR (CDCl3, d), 8.28–8.23
benzoyl chloride (0.370 g, 2.0 mmol) in dry acetone (50 cm3) was (m, 4H), 7.88 (d, J(H,H) = 8.8 Hz, 2H), 7.41 (d, J(H,H) = 8.5 Hz,
added dropwise a solution of KSeCN (0.288 g, 2.0 mmol) in dry 2H), 7.31 (s, 1H), 7.30–7.27 (m, 2H), 7.09 (d, J(H,H) = 8.5 Hz, 2H)
acetone (10 cm3) at room temperature. The mixture was stirred at ppm. 13C NMR (CDCl3, d), 173.7, 172.8, 149.9, 141.5, 138.6,
room temperature for 3 h, then 4-pentafluorosulfanylaniline (0.438 g, 135.5, 130.3, 130.2, 129.9, 129.0, 128.9, 128.7, 126.9, 123.4,
2.0 mmol) was added and the suspension was stirred in the dark at 119.7, 111.7 ppm. 77Se NMR (CDCl3, d), 624.7 ppm. 19F NMR
room temperature for another 18 h. After removing solvent in vacuo (CDCl3, d), 82.9 (pentet, 2J(F,F) = 152.1 Hz, 1F), 63.1 (d, 2J(F,F) =
the residue was purified by silica gel column chromatography (eluted 150.5 Hz, 4F) ppm. HRMS (CI+, m/z): found 605.9547 [M + H]+,
by dichloromethane) to give the products 8 and 9.
calculated mass for C22H13ClF5N3O3SSeH: 605.9552.
To a solution of 8 (0.475 g, 1.0 mmol) in dry acetone (10 cm3)
N-[4-(2,5-Dimethoxyphenyl)-3-(4-(pentafluoro-l6-sulfanyl)phenyl)-
was added 2-bromo-methylacetophenone (1.0 mmol), and the 1,3-selenazol-2(3H)-ylidene]-4-nitrobenzamide (10c). Yellow paste
mixture was stirred at room temperature for 24 h, then refluxed (0.568 g, 90%). M.p. 186–187 1C. Selected IR (KBr, cmÀ1): 1687,
for 3 h. After cooling to room temperature and removing the 1573, 1524, 1496, 1458, 1407, 1340, 1285, 1224, 1159, 1102, 1046,
solvent in vacuo, the residue was washed with water and extracted 1016, 909, 847, 771, 722, 664, 595. 1H NMR (CDCl3, d), 8.28–8.23
with dichloromethane (30 cm3 Â 3). The organic layers were (m, 4H), 7.82 (s, 1H), 7.76 (d, J(H,H) = 8.8 Hz, 2H), 7.41 (d, J(H,H) =
combined and dried over MgSO4. After removing solvent in vacuo, 8.5 Hz, 2H), 7.26 (s, 1H), 6.59 (d, J(H,H) = 8.0 Hz, 2H), 3.81 (s, 3H),
the residue was purified by silica gel column chromatography 3.39 (s, 3H) ppm. 13C NMR (CDCl3, d), 173.1, 172.6, 153.5, 150.4,
(eluted by 1 : 1 dichloromethane–hexane) to give 10a–d.
141.9, 141.1, 137.3, 130.1, 128.5, 128.4, 125.6, 124.0, 123.4, 121.3,
4-Nitro-N-[(4-(pentafluoro-l6-sulfanyl)phenyl)-carbamoselenoyl]- 119.6, 117.7, 116.0, 111.4, 55.8, 55.1 ppm. 77Se NMR (CDCl3, d),
benzamide (8). Deep red solid (0.750 g, 79%). M.p. 43–45 1C. 621.4 ppm. 19F NMR (CDCl3, d), 83.5 (pentet, J(F,F) = 151.9 Hz,
2
Selected IR (KBr, cmÀ1): 1683, 1599, 1526, 1407, 1346, 1263, 1F), 63.1 (d, J(F,F) = 150.1 Hz, 4F) ppm. HRMS (EI+, m/z): found
2
1
1145, 1101, 1013, 845, 714, 659, 595, 577. H NMR (CD2Cl2, d), 633.0160 [M]+, calculated mass for C24H18F5N3O5SSeH: 633.0165.
11.25 (s, 1H), 11.0 (s, 1H), 8.39 (d, J(H,H) = 8.8 Hz, 2H), 8.08 (d,
4-Nitro-N-[3-(4-(pentafluoro-l6-sulfanyl)phenyl)-4-(p-tolyl)-1,3-
J(H,H) = 8.5 Hz, 2H), 7.94 (d, J(H,H) = 8.5 Hz, 2H), 7.83 (d, J(H,H) = selenazol-2(3H)-ylidene]-benzamide (10d). Yellow solid (0.545 g,
8.5 Hz, 2H) ppm. 13C NMR (CD2Cl2, d), 207.9, 180.1, 165.4, 150.8, 93%). M.p. 189–190 1C. Selected IR (KBr, cmÀ1): 2359, 2338,
140.6, 136.5, 129.1, 128.6, 124.3, 119.8 ppm. 77Se NMR (CD2Cl2, d), 1675, 1599, 1578, 1524, 1453, 1407, 1331, 1275, 1191, 1161, 1100,
1
470.4 ppm. HRMS (EI+, m/z): found 474.9531 [M]+, calculated mass 1061, 1014, 901, 842, 720, 656, 597, 580. H NMR (CD2Cl2, d),
for C14H10F5N3O3SSe: 474.9528.
8.27–8.22 (m, 2H), 7.85 (d, J(H,H) = 8.8 Hz, 2H), 7.42 (d, J(H,H) =
4-Nitro-N-(5-((4-(pentafluoro-l6-sulfanyl)phenyl)amino)-3H- 8.8 Hz, 2H), 7.81 (d, J(H,H) = 9.1 Hz, 2H), 7.26 (s, 1H), 7.09 (d,
1,2,4-diselenazol-3-ylidene)benzamide (9). Yellow powder (0.110 g, J(H,H) = 8.0 Hz, 2H), 7.01 (d, J(H,H) = 8.5 Hz, 2H), 2.35 (s, 3H)
19%). M.p. 78–80 1C. Selected IR (KBr, cmÀ1): 1706, 1602, 1525, ppm. 13C NMR (CD2Cl2, d), 173.7, 172.6, 149.8, 141.7, 141.4,
1461, 1408, 1341, 1262, 1099, 1016, 843, 840, 718, 660, 575, 577. 140.0, 139.3, 130.1, 129.4, 129.1, 129.7, 128.5, 126.7, 126.6,
1H NMR (CD2Cl2, d), 8.35 (s, 1H), 7.91 (d, J(H,H) = 8.8 Hz, 2H), 7.73 123.4, 111.7, 21.3 ppm. 77Se NMR (CD2Cl2, d), 620.4 ppm. 19F
2
(d, J(H,H) = 8.8 Hz, 2H), 7.53 (d, J(H,H) = 8.2 Hz, 2H), 7.42 NMR (CD2Cl2, d), 83.1 (pentet, J(F,F) = 150.8 Hz, 1F), 62.8 (d,
(d, J(H,H) = 8.2 Hz, 2H) ppm. 13C NMR (CD2Cl2, d), 167.1, 164.2, 2J(F,F) = 149.4 Hz, 4F) ppm. HRMS (EI+, m/z): found 588.9995
162.2, 143.8, 141.3, 130.7, 129.6, 128.9, 123.7, 122.9, 117.9 ppm. [M]+, calculated mass for C23H16F5N3O3SSe: 588.9998.
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