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38% yield); mp 123–125 ꢀC; 1H NMR (300 MHz, DMSO-d6):
d 0.84 (t, J ¼ 6.4 Hz, 6H, 2CH3), 1.18–1.51 (m, 20H, 10CH2), 1.91–
2.07 (m, 4H, 2CH2), 4.68 (t, J ¼ 6.8 Hz, 4H, 2CH2N+), 7.31 (d, J ¼
8.7 Hz, 2H, 2CHpy), 7.65 (d, J ¼ 8.4 Hz, 4H, CHAr), 7.78 (t, J ¼
6.4 Hz, 2H, 2CHpy), 8.01 (d, J ¼ 8.4 Hz, 4H, CHAr), 8.50 (t, J ¼
8.7 Hz, 2H, 2CHpy), 9.04 (d, J ¼ 6.4 Hz, 2H, 2CHpy) ppm; 13C
NMR (75 MHz, DMSO-d6): d 13.9 (2C), 21.9 (2C), 25.6 (2C), 28.3
(2C), 28.4 (2C), 28.6 (2C), 31.1 (2C), 54.7 (2C), 113.5 (2C), 120.5
(2C), 121.6 (4C), 129.3 (4C), 138.1 (2C), 143.6 (2C), 148.4 (2C),
151.3 (2C), 158.8 (2C) ppm; m/z (%): 340 (100), 312 (14), 284 (7),
262 (6), 234 (4), 78 (8), 51 (3), 44 (2), 28 (4), 18 (6); nmax, (KBr):
2,20-[Biphenyl-4,40-diylbis(oxy)]bis(1-dodecylpyridinium)
dibromide (7, 2BP4BO-12,Br). C46H66Br2N2O2; Mw 838.9; white
solid (0.3 g, 36% yield); mp 190–192 ꢀC; 1H NMR (300 MHz,
DMSO-d6): d 0.83 (t, J ¼ 6.4 Hz, 6H, 2CH3), 1.18–1.49 (m, 36H,
18CH2), 1.91–2.02 (m, 4H, 2CH2), 4.64 (t, J ¼ 6.8 Hz, 4H,
2CH2N+), 7.30 (d, J ¼ 8.7 Hz, 2H, 2CHpy), 7.62 (d, J ¼ 8.4 Hz, 4H,
CHAr), 7.76 (t, J ¼ 6.4 Hz, 2H, 2CHpy), 8.01 (d, J ¼ 8.4 Hz, 4H,
CHAr), 8.47 (t, J ¼ 8.7 Hz, 2H, 2CHpy), 8.94 (d, J ¼ 6.4 Hz, 2H,
2CHpy) ppm; 13C NMR (75 MHz, DMSO-d6): d 13.8 (2C), 22.0
(2C), 25.6 (2C), 28.3 (2C), 28.6 (C), 28.7 (2C), 28.8 (4C), 28.9 (4C),
31.2 (2C), 54.7 (2C), 113.5 (2C), 120.5 (2C), 121.6 (4C), 129.3 (4C),
138.0 (2C), 143.5 (2C), 148.3 (2C), 151.4 (2C), 158.7 (2C) ppm; m/
z (%): 340 (74), 311 (9), 284 (6), 263 (3), 149 (8), 137 (56), 99 (3),
85 (4), 57 (10), 43 (100); nmax, (KBr): 3433, 2922, 2853, 1632, 1579,
3421, 2926, 2856, 1633, 1581, 1491, 1463, 1306, 1159, 781 cmꢁ1
.
2,20-[Biphenyl-4,40-diylbis(oxy)]bis(1-octylpyridinium)diiodide
(4, 2BP4BO-8,I). C38H50I2N2O2; Mw 820.6; yellow solid (0.39 g,
48% yield); mp 194–198 ꢀC; 1H NMR (300 MHz, DMSO-d6):
d 0.85 (t, J ¼ 6.4 Hz, 6H, 2CH3), 1.18–1.47 (m, 20H, 10CH2), 1.91–
2.05 (m, 4H, 2CH2), 4.64 (t, J ¼ 6.8 Hz, 4H, 2CH2N+), 7.31 (d, J ¼
8.7 Hz, 2H, 2CHpy), 7.63 (d, J ¼ 8.4 Hz, 4H, CHAr), 7.77 (t, J ¼
6.4 Hz, 2H, 2CHpy), 8.00 (d, J ¼ 8.4 Hz, 4H, CHAr), 8.46 (t, J ¼
8.7 Hz, 2H, 2CHpy), 8.92 (d, J ¼ 6.4 Hz, 2H, 2CHpy) ppm; 13C
NMR (75 MHz, DMSO-d6): d 13.9 (2C), 21.9 (2C), 25.6 (2C), 28.3
(2C), 28.4 (2C), 28.6 (2C), 31.1 (2C), 54.7 (2C), 113.5 (2C), 120.5
(2C), 121.6 (4C), 129.3 (4C), 138.1 (2C), 143.5 (2C), 148.4 (2C),
151.3 (2C), 158.8 (2C) ppm; m/z (%): 340 (100), 312 (16), 284 (9),
1490, 1464, 1298, 1154, 782 cmꢁ1
.
2,20-[Biphenyl-4,40-diylbis(oxy)]bis(1-dodecylpyridinium)
diiodide (8, 2BP4BO-12,I). C46H66I2N2O2; Mw 932.9; yellow solid
(0.54 g, 58% yield); mp 233–234 ꢀC; 1H NMR (300 MHz, DMSO-
d6): d 0.83 (t, J ¼ 6.4 Hz, 6H, 2CH3), 1.18–1.49 (m, 36H, 18CH2),
1.91–2.02 (m, 4H, 2CH2), 4.63 (t, J ¼ 6.8 Hz, 4H, 2CH2N+), 7.30
(d, J ¼ 8.7 Hz, 2H, 2CHpy), 7.62 (d, J ¼ 8.4 Hz, 4H, CHAr), 7.76 (t, J
¼ 6.4 Hz, 2H, 2CHpy), 8.00 (d, J ¼ 8.4 Hz, 4H, CHAr), 8.46 (t, J ¼
8.7 Hz, 2H, 2CHpy), 8.92 (d, J ¼ 6.4 Hz, 2H, 2CHpy) ppm; 13C
NMR (75 MHz, DMSO-d6): d 13.8 (2C), 21.9 (2C), 25.6 (2C), 28.3
(2C), 28.6 (C), 28.7 (4C), 28.8 (4C), 28.9 (2C), 31.2 (2C), 54.5 (2C),
113.5 (2C), 120.5 (2C), 121.6 (4C), 129.3 (4C), 138.0 (2C), 143.5
(2C), 148.3 (2C), 151.2 (2C), 158.8 (2C) ppm; m/z (%): 340 (100),
312 (16), 284 (14), 169 (6), 155 (6), 127 (7), 85 (23), 71 (10), 57
(14), 43 (11); nmax, (KBr): 3444, 2924, 2853, 1634, 1581, 1491,
262 (8), 240 (10), 206 (8), 71 (41), 57 (26), 43 (24), 29 (10); nmax
,
(KBr): 3442, 2926, 2855, 1633, 1581, 1490, 1308, 1194, 1156,
773 cmꢁ1
.
2,20-[Biphenyl-4,40-diylbis(oxy)]bis(1-decylpyridinium)
dibromide (5, 2BP4BO-10,Br). C42H58Br2N2O2; Mw 782.8; white
1
1462, 1306, 1157, 773 cmꢁ1
.
ꢀ
solid (0.33 g, 42% yield); mp 174–175 C; H NMR (300 MHz,
DMSO-d6): d 0.83 (t, J ¼ 6.4 Hz, 6H, 2CH3), 1.18–1.49 (m, 28H,
14CH2), 1.91–2.05 (m, 4H, 2CH2), 4.64 (t, J ¼ 6.8 Hz, 4H,
2CH2N+), 7.31 (d, J ¼ 8.7 Hz, 2H, 2CHpy), 7.63 (d, J ¼ 8.4 Hz, 4H,
CHAr), 7.77 (t, J ¼ 6.4 Hz, 2H, 2CHpy), 8.00 (d, J ¼ 8.4 Hz, 4H,
CHAr), 8.47 (t, J ¼ 8.7 Hz, 2H, 2CHpy), 8.95 (d, J ¼ 6.4 Hz, 2H,
2CHpy) ppm; 13C NMR (75 MHz, DMSO-d6): d 13.9 (2C), 21.9
(2C), 25.6 (2C), 28.3 (2C), 28.6 (2C), 28.7 (4C), 28.8 (2C), 31.2
(2C), 54.7 (2C), 113.5 (2C), 120.5 (2C), 121.6 (4C), 129.3 (4C),
138.1 (2C), 143.6 (2C), 148.4 (2C), 151.3 (2C), 158.8 (2C) ppm; m/
z (%): 340 (100), 312 (29), 284 (15), 262 (9), 234 (9), 137 (14), 78
(24), 71 (3), 55 (12), 41 (11); nmax, (KBr): 3433, 2923, 2854, 1632,
Preparation of 9
4,40-[Biphenyl-4,40-diylbis(oxy)]dipyridine
(4BP4BO).
The
mixture of 4,40-dihydroxy-1,10-biphenyl (1.86 g, 10 mmol), 4-
chloropyridine hydrochloride (3.00 g, 20 mmol), potassium
phosphate (16.96 g, 80 mmol), copper(I) iodide (1.90 g, 10
mmol) and picolinic acid (0.25 g, 2 mmol) in dry DMSO (50 mL)
was heated to 140 ꢀC for 72 hours in argon atmosphere. Solvent
was removed under reduced pressure, ethyl acetate (50 mL) was
added to crude residue, and the mixture was heated to reux for
1 hour. Then mixture was ltered. The organic ltrate was
concentrated under reduced pressure and the residue was
puried by recrystallization from heptane to afford 4,40-
[biphenyl-4,40-diylbis(oxy)]dipyridine (9) (2.89 g, 85% yield).
C22H16N2O2; Mw 340.4; white solid; mp 138–142 ꢀC; 1H NMR
(300 MHz, CDCl3): d 6.92 (d, J ¼ 6.9 Hz, 4H, 4CHpy), 7.20 (d, J ¼
8.4 Hz, 4H, 4CHAr), 7.65 (d, J ¼ 8.4 Hz, 4H, 4CHAr), 8.52 (d, J ¼
6.9 Hz, 4H, 4CHpy) ppm; 13C NMR (75 MHz, CDCl3): d 121.0 (4C),
128.6 (4C), 136.4 (4C), 138.3 (2C), 151.7 (2C), 153.2 (4C), 163.7
(2C) ppm.
1579, 1491, 1463, 1302, 1155, 782 cmꢁ1
.
2,20-[Biphenyl-4,40-diylbis(oxy)]bis(1-decylpyridinium)diiodide
(6, 2BP4BO-10,I). C42H58I2N2O2; Mw 876.8; yellow solid (0.35 g,
40% yield); mp 185–188 ꢀC; 1H NMR (300 MHz, DMSO-d6):
d 0.83 (t, J ¼ 6.4 Hz, 6H, 2CH3), 1.18–1.49 (m, 28H, 14CH2), 1.91–
2.05 (m, 4H, 2CH2), 4.64 (t, J ¼ 6.8 Hz, 4H, 2CH2N+), 7.31 (d, J ¼
8.7 Hz, 2H, 2CHpy), 7.63 (d, J ¼ 8.4 Hz, 4H, CHAr), 7.76 (t, J ¼
6.4 Hz, 2H, 2CHpy), 8.00 (d, J ¼ 8.4 Hz, 4H, CHAr), 8.46 (t, J ¼
8.7 Hz, 2H, 2CHpy), 8.92 (d, J ¼ 6.4 Hz, 2H, 2CHpy) ppm; 13C
NMR (75 MHz, DMSO-d6): d 13.8 (2C), 21.9 (2C), 25.6 (2C), 28.3
(2C), 28.6 (C), 28.7 (4C), 28.8 (2C), 31.2 (2C), 54.7 (2C), 113.5
(2C), 120.5 (2C), 121.6 (4C), 129.3 (4C), 138.0 (2C), 143.5 (2C),
148.3 (2C), 151.2 (2C), 158.8 (2C) ppm; m/z (%): 340 (28), 268
(25), 155 (22), 141 (22), 127 (14), 85 (89), 71 (70), 57 (100), 43 (93),
29 (39); nmax, (KBr): 3427, 2925, 2853, 1634, 1581, 1490, 1462,
Preparations of 10–15. Alkyl halide (2.2 mmol) was added to
solution of 4,40-[biphenyl-4,40-diylbis(oxy)]dipyridine (9)
a
(0.34 g, 1 mmol) in acetonitrile (3 mL). The mixture was heated
under reux for 72 h, then allowed to cool to room temperature
and ltered off. The solid was washed with 10 mL of cold
acetone and dried to give a bis-QAC. The yields of bis-QACs 10–
15 were 36–58% depend on alkyl halide.
1307, 1156, 772 cmꢁ1
.
© 2021 The Author(s). Published by the Royal Society of Chemistry
RSC Adv., 2021, 11, 3429–3438 | 3433