L. G. Bahrin et al. / Bioorg. Med. Chem. xxx (2016) xxx–xxx
7
8
1
2.4, 94.9, 119.8, 126.9, 127.6, 128.9, 129.56, 136.3, 137.3, 137.4,
58.8, 186.7, 191.1 ppm. EI-MS (m/z, M ): 531.0. IR-ATR (cm ):
NMR (75 MHz, DMSO-d
117.8, 118.8, 119.4, 127.6, 128.0, 129.5, 129.6, 130.5, 137.0,
6
): d 10.6, 10.8, 54.6, 54.7, 75.8, 112.0,
+
ꢁ1
+
19FNOS+
m
ꢀ = 1576, 1543,
m
ꢀ = 2975, 2762, 1685, 1603, 1467, 1418, 1266, 1201, 999, 807,
26, 508. Anal. (C20 19ClINO ) found (calcd): C, 45.17 (45.48);
H, 3.60 (3.71); N, 2.63 (2.97).
147.7, 157.6, 184.8. ESI-MS (m/z, MꢁBF
4
] ): calcd for C20
H
2
:
ꢁ1
6
H
S
2 2
372.08866, found: 372.08754. IR-ATR (cm ):
1283, 1182, 1047, 763, 708.
4
.2.17. 2-N,N-Diethylamino-4-phenyl-4H-1,3-dithiol[4,5-c]
4.2.22. 2-N,N-Diethylamino-8-fluoro-4-(4-fluorophenyl)-4H-
1,3-dithio[4,5-c]chromen-2-ylium tetrafluoroborate (5g)
Colorless crystals, 110 mg, 77%. Mp = 211–212 °C. 1H NMR
chromen-2-ylium tetrafluoroborate (5a)
To a mixture of sulfuric acid (0.25 mL) and acetic acid (0.75 mL),
flavanone 4a (111 mg, 0.3 mmol) was added and the resulting
solution was heated to 80 °C for 20 min. The reaction mixture
was then left to cool to room temperature and a solution of sodium
tetrafluoroborate (110 mg) in water (5 mL) was added dropwise,
with vigorous stirring. The resulting precipitate was then filtered,
washed thoroughly with water and recrystallized from ethanol,
6
(300 MHz, DMSO-d ): d 1.32 (t, 3H), 1.41 (t, 3H), 3.82–3.99 (m,
3
4
4H), 6.79 (s, 1H), 7.10 (dd, 1H, J = 9.0 Hz, J = 4.6 Hz), 7.21–7.27
(m, 1H), 7.28–7.35 (m, 2H), 7.50 (dd, 1H, J = 8.5 Hz, 4J = 2.9 Hz),
7.55–7.61 (m, 2H) ppm. C NMR (75 MHz, DMSO-d ): d 10.6,
6
3
1
3
10.8, 54.6, 54.7, 75.1, 112.0, 116.5, 117.7, 118.9, 119.4, 127.8,
129.3, 130.6, 133.3, 147.5, 157.6, 163.3, 184.8 ppm. ESI-MS (m/z,
+
+
yielding the desired product in the form of colorless crystals
MꢁBF
4
] ): calcd for C20
H
18
F
2
NOS
2
: 390.07924, found: 390.07941.
1
ꢁ1
(
100 mg, 77%). Mp >220 °C. H NMR (300 MHz, DMSO-d
6
): d 1.31
IR-ATR (cm ):
m
ꢀ = 1606, 1539, 1510, 1470, 1284, 1229, 1160,
(
t, 3H), 1.40 (t, 3H), 3.80–4.00 (m, 4H), 6.78 (s, 1H), 7.05–7.09 (m,
1046, 988, 821, 764, 521.
1
7
5
1
H), 7.11–7.16 (m, 1H), 7.36–7.41 (m, 1H), 7.44–7.49 (m, 4H),
1
3
6
.50–7.55 (m, 2H). C NMR (75 MHz, DMSO-d ): d 10.7, 10.8,
4.2.23. 2-N,N-Diethylamino-8-fluoro-4-(4-chlorophenyl)-4H-
1,3-dithio[4,5-c]chromen-2-ylium tetrafluoroborate (5h)
Colorless crystals, 114 mg, 77%. Mp = 129–130 °C. 1H NMR
4.5, 54.7, 75.7, 116.8, 117.7, 123.6, 125.3, 127.8, 128.0, 128.4,
+
29.6, 130.4, 132.6, 137.4, 151.5, 184.9. ESI-MS (m/z, MꢁBF
4
] ):
: 354.09863, found: 406.09921. IR-ATR
ꢀ = 1603, 1539, 1448, 1199, 1045, 1034, 761, 519.
+
calcd for C20
H
20NOS
2
(300 MHz, DMSO-d
4H), 6.80 (s, 1H), 7.11 (dd, 1H, J = 9.0 Hz, J = 4.6 Hz), 7.20–7.28
6
): d 1.32 (t, 3H), 1.41 (t, 3H), 3.81–3.99 (m,
ꢁ1
3
4
(
cm ):
m
3
4
(
m, 1H), 7.50 (dd, 1H, J = 8.5 Hz, J = 2.9 Hz), 7.52–7.56 (m, 4H)
1
3
4
.2.18. 2-N,N-Diethylamino-4-(4-fluorophenyl)-4H-1,3-dithio
ppm. C NMR (75 MHz, DMSO-d
6
): d 10.1, 10.3, 54.1, 54.3, 74.5,
[
4,5-c]chromen-2-ylium tetrafluoroborate (5b)
111.6, 117.2, 118.4, 118.9, 127.9, 128.5, 129.1, 129.5, 134.6,
Colorless crystals, 77 mg (56%). Mp = 209–211 °C. 1H NMR
135.5, 146.9, 157.2, 184.4 ppm. ESI-MS (m/z, MꢁBF
] ): calcd for
: 406.04969, found: 406.05015. IR-ATR (cm ):
+
4
+
ꢁ1
(
4
(
300 MHz, DMSO-d
H), 6.79 (s, 1H), 7.04–7.09 (m, 1H), 7.11–7.18 (m, 1H), 7.28–7.35
m, 2H), 7.36–7.42 (m, 1H), 7.44–7.49 (m, 1H), 7.54–7.62 (m,
6
): d 1.32 (t, 3H), 1.40 (t, 3H), 3.80–4.00 (m,
C
20
H
18FClNOS
2
m
ꢀ = 1604, 1538, 1469, 1281, 1182, 1047, 990, 832, 767, 434.
1
3
2
1
1
H). C NMR (75 MHz, DMSO-d
6
): d 10.7, 10.8, 54.5, 54.7, 74.9,
4.2.24. 2-N,N-Diethylamino-8-fluoro-4-(4-bromophenyl)-4H-
1,3-dithio[4,5-c]chromen-2-ylium tetrafluoroborate (5i)
Colorless crystals, 111 mg, 69%. Mp = 147–148 °C. 1H NMR
16.5, 116.8, 117.8, 123.6, 125.3, 127.6, 128.6, 130.5, 132.7,
+
33.7, 151.3, 163.3, 184.9. ESI-MS (m/z, M–BF
4
] ): calcd for C20
H
19
+
ꢁ1
FNOS
1
2
: 372.08866, found: 372.08792. IR-ATR (cm ):
m
ꢀ = 1599,
(300 MHz, DMSO-d
6.79 (s, 1H), 7.11 (dd, 1H, J = 9.0 Hz, J = 4.6 Hz), 7.20–7.28 (m, 1H),
6
): d 1.32 (t, 3H), 1.41 (t, 3H), 3.82–3.98 (m, 4H),
3
4
539, 1448, 1215, 1161, 1031, 847, 779, 520.
3
4
7
.44–7.49 (m, 2H), 7.50 (dd, 1H, J = 8.5 Hz, J = 2.9 Hz), 7.65–7.70
1
3
4
.2.19. 2-N,N-Diethylamino-4-(4-bromophenyl)-4H-1,3-dithio
(m, 2H) ppm. C NMR (75 MHz, DMSO-d
6
): d 10.1, 10.32, 54.1,
[
4,5-c]chromen-2-ylium tetrafluoroborate (5d)
54.3, 74.5, 111.6, 117.2, 118.4, 118.9, 123.4, 127.4, 128.4, 129.7,
Colorless crystals, 96 mg (62%). Mp = 179–181 °C. 1H NMR
132.0, 135.9, 146.9, 157.2, 184.4 ppm. ESI-MS (m/z, MꢁBF
] ): calcd
+
4
+
ꢁ1
(
4
(
300 MHz, DMSO-d
H), 6.79 (s, 1H), 7.06–7.09 (m, 1H), 7.12–7.17 (m, 1H), 7.37–7.42
m, 1H), 7.44–7.49 (m, 3H), 7.66–7.70 (m, 2H). 13C NMR (75 MHz,
DMSO-d ): d 10.7, 10.8, 54.5, 54.7, 74.9, 116.8, 117.8, 123.7,
23.8, 125.3, 127.2, 128.7, 130.2, 132.5, 132.7, 136.7, 151.2,
6
): d 1.32 (t, 3H), 1.40 (t, 3H), 3.82–3.99 (m,
for C20
H
18FBrNOS
2
: 449.99917, found: 450.00022. IR-ATR (cm ):
m
ꢀ = 1605, 1538, 1469, 1282, 1181, 1047, 990, 831, 766, 520.
6
4.2.25. 2-N,N-Diethylamino-8-fluoro-4-(4-iodophenyl)-4H-1,3-
dithio[4,5-c]chromen-2-ylium tetrafluoroborate (5j)
1
1
4
1
+
+
Colorless crystals, 155 mg, 88%. Mp = 167–168 °C. 1H NMR
84.9. ESI-MS (m/z, MꢁBF
4
] ): calcd for
C
20
H
19BrNOS
2
:
ꢁ1
32.00859, found: 432.00942. IR-ATR (cm ):
449, 1216, 1031, 847, 770, 521.
m
ꢀ = 1598, 1537,
(300 MHz, DMSO-d
6
): d 1.32 (t, 3H), 1.40 (t, 3H), 3.82–3.99 (m,
3
4
4H), 6.76 (s, 1H), 7.10 (dd, 1H, J = 9.0 Hz, J = 4.6 Hz), 7.21–7.27
3
(
m, 1H), 7.28–7.33 (m, 2H), 7.49 (dd, 1H, J = 8.5 Hz, 4J = 2.9 Hz),
1
3
4
.2.20. 2-N,N-Diethylamino-4-(4-iodophenyl)-4H-1,3-dithio
7.81–7.87 (m, 2H) ppm. C NMR (75 MHz, DMSO-d
6
): d 10.6, 10.8,
[
4,5-c]chromen-2-ylium tetrafluoroborate (5e)
54.6, 54.7, 75.2, 97.4, 112.0, 117.7, 118.9, 119.4, 127.8, 128.8,
Colorless crystals, 119 mg (70%). Mp = 129–130 °C. 1H NMR
130.2, 136.7, 138.4, 147.4, 157.7, 184.8 ppm. ESI-MS (m/z, MꢁBF
] ):
: 497.98530, found: 497.98445. IR-ATR
(cm ): m
ꢀ = 1602, 1537, 1281, 1182, 1049, 1007, 830, 766, 520.
+
4
+
(
4
(
300 MHz, DMSO-d
H), 6.76 (s, 1H), 7.04–7.09 (m, 1H), 7.11–7.16 (m, 1H), 7.28–7.33
m, 2H), 7.37–7.42 (m, 1H), 7.44–7.47 (m, 1H), 7.81–7.86 (m,
6
): d 1.32 (t, 3H), 1.40 (t, 3H), 3.83–3.99 (m,
calcd for C20H18FINOS
2
ꢁ1
1
3
2
9
1
4
1
H). C NMR (75 MHz, DMSO-d
6
): d 10.7, 10.8, 54.5, 54.7, 75.1,
4.2.26. 2-N,N-Diethylamino-8-chloro-4-phenyl-4H-1,3-dithio
[4,5-c]chromen-2-ylium tetrafluoroborate (5k)
7.3, 116.8, 117.8, 123.7, 125.3, 127.2, 128.6, 130.1, 132.7, 137.1,
+
+
Colorless crystals, 103 mg (72%). Mp >220 °C. 1H NMR
38.4, 151.2, 184.9. ESI-MS (m/z, MꢁBF
4
] ): calcd for C20
H
19INOS
2
:
ꢁ1
79.99473, found: 479.99596. IR-ATR (cm ):
449, 1289, 1033, 765.
m
ꢀ = 1598, 1540,
(300 MHz, DMSO-d
6
): d 1.31 (t, 3H), 1.40 (t, 3H), 3.82–3.97 (m,
3
3
4H), 6.82 (s, 1H), 7.10 (d, 1H, J = 8.7 Hz), 7.43 (dd, 1H, J = 8.7 Hz,
4
4
13
J = 2.5 Hz), 7.46–7.53 (m, 5H), 7.65 (d, 1H, J = 2.5 Hz). C NMR
(75 MHz, DMSO-d ): d 10.6, 10.8, 54.6, 54.8, 75.9, 118.3, 119.5,
124.8, 127.1, 127.3, 128.0, 129.3, 129.6, 130.5, 132.0, 137.0,
4
.2.21. 2-N,N-Diethylamino-8-fluoro-4-phenyl-4H-1,3-dithio
6
[
4,5-c]chromen-2-ylium tetrafluoroborate (5f)
1
+
19ClNOS+
m
ꢀ = 1595, 1539,
Colorless crystals, 91 mg (66%). Mp >220 °C. H NMR (300 MHz,
150.2, 184.8. ESI-MS (m/z, MꢁBF
4
] ): calcd for C20
H
2
:
ꢁ1
DMSO-d
1
6
): d 1.31 (t, 3H), 1.40 (t, 3H), 3.81–3.97 (m, 4H), 6.78 (s,
388.05911, found: 388.05804. IR-ATR (cm ):
1468, 1282, 1197, 1034, 771, 701, 560.
1
3
H), 7.10–7.13 (m, 1H), 7.22–7.27 (m, 1H), 7.45–7.54 (m, 6H).
C