Syntheses Pyridinium Phenoxides as Model Compounds in Nonlinear Optics
4-[4-(Methoxymethoxy)-2,3,5,6-tetramethylphenyl]pyridine (22f):
8.56 (d, J = 6 Hz, 2 H) ppm. 13C NMR (CD3OD): δ = 15.9, 27.7,
FULL PAPER
Crude 22f was obtained from protected bromophenol 20f (136 mg,
0.5 mmol) following procedure E. Pure 20f was obtained after
113.8, 127.8, 130.4, 144.0, 149.9, 152.1, 158.6 ppm. IR (KBr): ν =
834, 855, 866, 939, 997, 1065, 1157, 1205, 1216, 1244, 1259, 1284
1306, 1325, 1339, 1376, 1412, 1446, 1459, 1539, 1578, 1603, 2872,
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chromatography (cyclohexane/AcOEt, 6:4) as colourless crystals
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(107 mg, 79%). M.p. 74 °C. H NMR (CDCl3): δ = 1.88 (s, 6 H), 2933, 2974, 3038, 3122, 3454 cm–1. C15H17NO (227.31): C 79.26, H
2.24 (s, 6 H), 3.66 (s, 3 H), 4.96 (s, 2 H), 7.14 (d, J = 5.5 Hz, 2 H),
8.67 (d, J = 5.5 Hz, 2 H) ppm. 13C NMR (CDCl3): δ = 14.0, 18.2,
58.1, 99.9, 125.5, 127.6, 132.8, 136.1, 150.3, 151.4, 154.3 ppm. IR
7.54, N 6.16; found C 79.23, H 7.54, N 6.05.
3,5-Diisopropyl-4-(pyridin-4Ј-yl)phenol (23e): Crude 23e, obtained
from 22e (200 mg, 0.7 mmol) following procedure F, was purified
by sublimation (170 °C, 1 Torr) to give a colourless solid (105 mg,
(KBr): ν = 527, 641, 823, 925, 971, 989, 1050, 1078, 1101, 1156,
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1216, 1267, 1384, 1402, 1415, 1465, 1541, 1596, 2875, 2924,
2942 cm–1. C17H21NO2 (271.35): C 75.25, H 7.80, N 5.16; found C
75.24, H 7.88, N 5.01.
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62%). M.p. 240 °C. H NMR (CD3OD): δ = 1.06 (d, J = 6.8 Hz,
12 H), 2.45 (sept, 6.8 Hz, 2 H), 6.66 (s, 2 H), 7.25 (d, J = 5.8 Hz,
2 H), 8.56 (d, J = 5.8 Hz, 2 H) ppm. 13C NMR (CD3OD): δ = 24.3,
31.6, 110.7, 127.7, 129.3, 148.7, 149.8, 152.5, 158.9 ppm. IR (KBr):
4-[4-(Methoxymethoxy)-3,5-dimethylphenyl]pyridine (22g): Crude
22g was obtained from protected bromophenol 20g (470 mg,
1.9 mmol) following procedure E. The crude product was purified
by chromatography (cyclohexane/AcOEt, 7:3) as colourless crystals
ν = 569, 838, 1066, 1183, 1213, 1306, 1328, 1344, 1413, 1448, 1468,
˜
1580, 1605, 2618, 2660, 2725, 2869, 2926 cm–1. C17H21NO (255.35):
C 79.96, H 8.29, N 5.49; found C 79.68%, H 8.22, N 5.41.
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(443 mg, 95%). M.p. 46 °C. H NMR (CDCl3): δ = 2.38 (s, 6 H),
2,3,5,6-Tetramethyl-4-(pyridin-4Ј-yl)phenol (23f): Crude 23f, ob-
tained from 22f (271 mg, 1 mmol) following procedure F, was puri-
fied by sublimation (180 °C, 1 Torr) to give a colourless solid
(156 mg, 68%). M.p. 270 °C. 1H NMR (CD3OD): δ = 1.86 (s, 6
H), 2.18 (s, 6 H), 7.17 (d, J = 4.3 Hz, 2 H), 8.55 (d, J = 4.3 Hz, 2
H) ppm. 13C NMR (CD3OD): δ = 12.8, 17.9, 122.4, 127.4, 132.1,
3.64 (s, 3 H), 5.01 (s, 2 H), 7.31 (s, 2 H), 7.48 (d, J = 4.5 Hz, 2 H),
8.62 (d, J = 4.5 Hz, 2 H) ppm. 13C NMR (CDCl3): δ = 17.2, 57.6,
99.3, 121.6, 127.7, 132.0, 133.9, 148.3, 150.1, 156.1 ppm. IR (KBr):
ν = 493, 570, 639, 718, 820, 920, 963, 1072, 1156, 1174, 1214, 1221,
˜
1240, 1328, 1398, 1422, 1437, 1457, 1479, 1544, 1597, 2925,
2959 cm–1. C15H17NO2 (243.3): C74.05, H 7.04, N 5.76; found C
74.45, H 7.09, N 5.69.
132.7, 149.9, 153.5, 154.3 ppm. IR (KBr): ν = 528, 647, 823, 1005,
˜
1032, 1070, 1086, 1099, 1173, 1212, 1249, 1283, 1305, 1403, 1418,
1449, 1602, 2937, 2989, 3041, 3125. cm–1 C15H17NO (227.29): C
79.26, H 7.54, N 6.16; found C 79.25, H 7.53, N 6.06.
4-(Pyridin-4Ј-yl)phenol (23a): The crude product, obtained from
22a (890 mg, 4.13 mmol) following procedure F, was purified by
recrystallization from EtOH (573 mg, 81%) and can be sublimated
(180 °C, 1 Torr) to obtain a colourless solid. M.p. 256 °C. 1H NMR
(CD3OD): δ = 6.91 (d, J = 8.5 Hz, 2 H), 7.62 (d, J = 8.5 Hz, 2 H),
7.63 (d, J = 5.6 Hz, 2 H), 8.49 (d, J = 5.6 Hz, 2 H) ppm. 13C NMR
(CD3OD): δ = 117.1, 122.2, 129.3, 129.5, 150.3, 150.6, 160.4 ppm.
2,6-Dimethyl-4-(pyridin-4Ј-yl)phenol (23g): Crude 23g, obtained
from 22g (180 mg, 0.74 mmol) following procedure F, was purified
by sublimation (150 °C, 1 Torr) to give a colourless solid (109 mg,
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74%). M.p. 201 °C. H NMR (CD3OD): δ = 2.29 (s, 6 H), 7.36 (s,
2 H), 7.64 (d, J = 6 Hz, 2 H), 8.47 (d, J = 6 Hz, 2 H) ppm. 13C
NMR (CD3OD): δ = 16.7, 122.3, 126.3, 128.0, 129.5, 150.2, 150.9,
IR (KBr): ν = 495, 502, 574, 726, 816, 1000, 1029, 1174, 1181,
˜
1223, 1255, 1283, 1295,1398, 1414, 1450, 1490, 1520, 1583, 1600,
2581, 2904 cm–1. C11H9NO (171.07): C 77.17, H 5.3, N 8.18; found
C 77.34, H 5.35, N 8.15.
156.3 ppm. IR (KBr): ν = 643, 819, 829, 1197, 1218, 1268, 1309,
˜
1332, 1428, 1479, 1594, 2916 cm–1. C13H13NO (199.24): C 78.36, H
6.58, N 7.03; found C 78.69, H 6.73, N 6.94.
3-Methyl-4-(pyridin-4Ј-yl)phenol (23b): The crude product, ob-
tained from 22b (72 mg, 0.31 mmol) following procedure F, was
purified by sublimation (160 °C, 1 Torr) to give a colourless solid
(35 mg, 60%). M.p. 206 °C. 1H NMR (CD3OD): δ = 2.23 (s, 3 H),
6.71 (dd, J = 8, 2.4 Hz, 1 H), 6.74 (d, J = 2.4 Hz, 1 H), 7.07 (d, J
= 8 Hz, 1 H), 7.37 (dd, J = 4.8, 1.6 Hz, 2 H), 8.51 (dd, J = 4.8,
1.6 Hz, 2 H) ppm. 13C NMR (CD3OD): δ = 20.6, 114.3, 118.4,
4-(4Ј-Hydroxyphenyl)-1-methylpyridinium Iodide (24a): Crude 24a
was synthesized from 23a (100 mg, 0.58 mmol) following procedure
G. After recrystallization from EtOH pure 24a was obtained as a
colourless solid (120 mg, 65%) and only characterized by NMR
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spectroscopy. H NMR (CD3OD): δ = 4.33 (s, 3 H), 7.00 (d, J =
8.8 Hz, 2 H), 7.92 (d, J = 8.8 Hz, 2 H), 8.27 (d, J = 6.5 Hz, 2 H),
8.73 (d, J = 6.5 Hz, 2 H) ppm. 13C NMR (CD3OD): δ = 47.8,
117.8, 124.0, 125.4, 131.1, 146.0, 156.9, 163.4 ppm.
126.2, 131.2, 131.7, 137.6, 149.6, 152.6, 159.0 ppm. IR (KBr): ν =
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813, 1005, 1025, 1173, 1220, 1247, 1288, 1304, 1417, 1468, 1487,
1509, 1544, 1574, 1604, 2481, 2518, 2537, 2591, 2593, 2597, 2639,
2684, 2780, 2786, 2871, 2879, 2890, 2923, 2983 cm–1. HRMS (ESI-
Q-Tof): calcd. for C12H11NO [M]·+ 185.0841; found 185.0842.
4-(4Ј-Hydroxy-2Ј-methylphenyl)-1-methylpyridinium Iodide (24b):
Compound 24b was synthesized from 23b (212 mg, 1.14 mmol) fol-
lowing procedure G and was obtained as a colourless solid
(356 mg, 95%). Iodide 24b was only characterized by NMR spec-
troscopy. 1H NMR (CD3OD): δ = 2.38 (s, 3 H), 4.24 (s, 3 H), 6.56–
6.58 (m, 2 H), 7.26 (d, J = 9.3 Hz, 1 H), 7.88 (d, J = 6.8 Hz, 2 H),
8.52 (d, J = 6.8 Hz, 2 H) ppm. 13C NMR (CD3OD): δ = 21.8, 47.1,
119.6, 120.8, 123.8, 126.5, 133.8, 139.5, 144.3, 159.7, 173.9 ppm.
3,5-Dimethyl-4-(pyridin-4Ј-yl)phenol (23c): Crude 23c, obtained
from 22c (1.17 g, 4.81 mmol) following procedure F, was purified
by sublimation (180 °C, 1 Torr) to give a colourless solid (767 mg,
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80%). M.p. 270 °C. H NMR (CD3OD): δ = 1.95 (s, 6 H), 6.57 (s,
2 H), 7.21 (d, J = 5 Hz, 2 H), 8.65 (d, J = 5 Hz, 2 H) ppm. 13C
NMR (CDCl3): δ = 20.8, 115.4, 127.3, 131.5, 137.4, 150.2, 152.5,
4-(4Ј-Hydroxy-2Ј,6Ј-dimethylphenyl)-1-methylpyridinium
Iodide
(24c): Compound 24c was synthesized from 23c (500 mg, 2.5 mmol)
following procedure G and was obtained as a colourless solid
(556 mg, 65%). Iodide 24c was only characterized by NMR spec-
158.1 ppm. IR (KBr): ν = 607, 726, 833, 850, 858, 996, 1036, 1068,
˜
1156, 1213, 1241, 1257, 1276, 1310, 1412, 1440, 1465, 1542, 1585,
1605, 1611, 3043 cm–1. HRMS (ESI-Q-Tof): calcd. for C13H13NO
[M]·+ 199.0997; found 199.0977.
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troscopy. H NMR (CD3OD): δ = 2.05 (s, 6 H), 4.45 (s, 3 H), 6.65
(s, 2 H), 7.94 (d, J = 6.5 Hz, 2 H), 8.91 (d, J = 6.5 Hz, 2 H) ppm.
13C NMR (CD3OD): δ = 20.9, 48.7, 116.1, 128.6, 131.0, 137.7,
146.4, 159.5, 160.9 ppm.
3,5-Diethyl-4-(pyridin-4Ј-yl)phenol (23d): Crude 23d, obtained from
22d (271 mg, 1 mmol) following procedure F, was purified by subli-
mation (180 °C, 1 Torr) to give a colourless solid (199 mg, 87%).
M.p. 230 °C. 1H NMR (CD3OD): δ = 0.99 (t, J = 7.6 Hz, 6 H),
2.24 (q, J = 7.6 Hz, 4 H), 6.60 (s, 2 H), 7.26 (d, J = 6 Hz, 2 H),
4-(2Ј,6Ј-Diethyl-4Ј-hydroxyphenyl)-1-methylpyridinium Iodide (24d):
Compound 24d was synthesized from 23d (200 mg, 0.88 mmol) fol-
Eur. J. Org. Chem. 2006, 2727–2738
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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