The Journal of Organic Chemistry
NOTE
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(0.5448 mmol) of 4-ethynyl-N,N-dimethylbenzenamine B, 0.1135 g
(0.4267 mmol) of the title compound was isolated as a red solid. Yield
86%; mp 209-212 °C; IR (KBr) 3095, 2909, 2208, 1609, 1586, 1529,
1508, 1371, 1336, 1104, 820 cm-1; 1H NMR (CDCl3; 400 MHz) δ 3.00
(6H, s), 6.65 (2H, d, J = 8.8 Hz), 7.41 (2H, d, J = 8.4 Hz), 7.57 (2H, d, J =
9.2 Hz), 8.16 (2H, d, J = 8.4 Hz); 13C NMR (CDCl3; 100 MHz) δ 40.3,
86.6, 97.3, 111.9, 123.8, 128.7, 128.8, 131.8, 132.1, 132.2, 132.3, 133.4,
133.8, 146.4, 150.9; ESI-TOF-MS m/z 267 [M þ H]þ; HRMS calcd for
C16H15N2O2 ([M þ H]þ) 267.1134, found 267.1130.
832 cm-1; H NMR (CDCl3; 400 MHz) δ 7.46-7.52 (4H, m), 7.67
(1H, t, J = 7.6 Hz), 7.77 (1H, d, J = 7.6 Hz), 8.30 (1H, d, J = 8.0 Hz), 8.38
(1H, d, J = 6.8 Hz), 8.51 (1H, d, J = 8.0 Hz); ESI-TOF-MS m/z 324
[M þ H]þ; HRMS calcd for C21H10NO3 ([M þ H]þ) 324.0660, found
324.0653.
Synthesis of 4-(2-(4-(N,N-dimethylamino)phenyl)ethynyl)-1,
8-naphthalic anhydride (5B): Using the general procedure, starting
from 0.06 g (0.2166 mmol) of 4-bromo-1,8-naphthalicanhydride 5 and
0.0345 g (0.2382 mmol) of 4-ethynyl-N,N-dimethylbenzenamine B,
0.0635 g (0.1862 mmol) of the title compound was isolated as a red
solid. Yield 86%; mp 288-292 °C; IR (KBr) 2917, 2862, 2188, 1752,
1730, 1604, 1585, 1575, 1524, 1371, 1169, 1010, 781 cm-1; 1H NMR
(CDCl3; 400 MHz) δ 3.06 (6H, s), 6.82 (2H, bs), 7.55 (2H, d, J =
7.6 Hz), 7.84-7.92 (2H, m), 8.53 (1H, d, J = 7.6 Hz), 8.64 (1H, d, J =
7.2 Hz), 8.81 (1H, d, J = 8.0 Hz); 13C NMR (CDCl3; 100 MHz) δ 40.1,
85.2, 103.8, 107.9, 110.6, 111.7, 112.1, 112.8, 118.9, 125.3, 127.5, 129.5,
130.5, 132.8, 133.5, 134.2, 135.0, 153.4, 160.4, 160.8; ESI-TOF-MS m/z
342 [M þ H]þ; HRMS calcd for C22H16NO3 ([M þ H]þ) 342.1130,
found 342.1125.
Synthesis of 4-(2-(9-bromoanthracen-10-yl)ethynyl)ben-
zonitrile (6A): Using the general procedure, starting from 0.070 g
(0.2083 mmol) of 9,10-dibromoanthracene 6 and 0.0265 g (0.2083
mmol) of 4-ethynylbenzonitrile A, 0.040 g (0.1190 mmol) of 9,10-
dibromoanthracene was isolated as unreacted and 0.0245 g (0.0641
mmol) of the title compound was isolated as a yellow solid. Yield 72%;
mp 214-215 °C; IR (KBr) 2222, 2198, 1620, 1602, 1502, 837, 752
cm-1; 1H NMR (CDCl3; 400 MHz) δ 7.62-7.64 (4H, m), 7.70 (2H,
dd, J = 1.6, 8.2 Hz), 7.80 (2H, dd, J = 1.2, 8.0 Hz), 8.55-8.60 (4H, m);
13C NMR (CDCl3; 100 MHz) δ 90.6, 100.0, 112.0, 118.7, 127.0, 127.5,
127.8, 128.4, 128.7, 129.1, 130.5, 132.2, 132.5, 133.4, 142.5; ESI-TOF-
MS m/z 383, 385 [M þ H]þ; HRMS calcd for C23H12N ([M - Br])
302.0970, found 302.0960.
Synthesis of 6-chloro-3-(2-(4-(N,N-dimethylamino)phenyl)
ethynyl)picolinonitrile (3B): Using the general procedure, start-
ing from 0.05 g (0.2299 mmol) of 3-bromo-6-chloropicolinonitrile 3
and 0.04 g (0.2758 mmol) of 4-ethynyl-N,N-dimethylbenzenamine B,
0.0393 g (0.1396 mmol) of the title compound was isolated as a yellow
solid. Yield 61%; mp 142-145 °C; IR (KBr) 2923, 2853, 2193, 1606,
1560, 1527, 1369, 1156, 1023, 808 cm-1; 1H NMR (CDCl3; 400 MHz)
δ 3.01 (6H, s), 6.64 (2H, d, J = 8.8 Hz), 7.42-7.47 (3H, m), 7.77 (1H, d,
J = 8.8 Hz); 13C NMR (CDCl3; 100 MHz) δ 40.2, 81.3, 103.3, 107.4,
111.8, 115.5, 125.6, 127.6, 130.4, 133.7, 140.9, 149.4, 151.3; ESI-TOF-
MS m/z 282 [M þ H]þ; HRMS calcd for C16H13N3Cl ([M þ H]þ)
282.0798, found 282.0789.
From the same reaction mixture we were able to isolate 0.0224 g
(0.0574 mmol) of dihalide (Br and Cl) substituted compound, 3,6-
bis(2-(4-(N,N-dimethylamino)phenyl)ethynyl)picolinonitrile, 3B0 as a
yellow solid. Yield 25%; mp 210-212 °C; IR (KBr) 2922, 2852, 2201,
1604, 1530, 1447, 1365, 1157, 816 cm-1; 1H NMR (CDCl3; 400 MHz)
δ 2.99 (12H, d, J = 1.6 Hz), 6.63 (4H, d, J = 8.8 Hz), 7.45 (2H, d, J =
3.2 Hz), 7.47 (2H, d, J = 3.2 Hz), 7.50 (1H, d, J = 8.4 Hz), 7.73 (1H, d, J =
8.4 Hz); 13C NMR (CDCl3; 100 MHz) δ 40.3, 82.7, 86.7, 95.5, 102.8,
107.9, 108.0, 109.9, 111.9, 116.2, 124.1, 128.8, 133.7, 133.8, 135.5, 138.4,
142.9, 151.1, 151.2; ESI-TOF-MS m/z 391 [M þ H]þ; HRMS calcd for
C26H23N4 ([M þ H]þ) 391.1922, found 391.1930.
Synthesis of 4-(2-(2,5-dimethoxyphenyl)ethynyl)benzo-
nitrile (4A): Using the general procedure, starting from 0.030 g
(0.1382 mmol) of 2-bromo-1,4-dimethoxybenzene 4 and 0.021 g
(0.1653 mmol) of 4-ethynylbenzonitrile A, 0.026 g (0.0988 mmol) of
the title compound was isolated as a white semisolid. Yield 72%; IR
(KBr) 2924, 2853, 2227, 1602, 1494, 1458, 1261, 1021, 840, 805,
699 cm-1; 1H NMR (CDCl3; 400 MHz) δ 3.77 (3H, s), 3.86 (3H, s),
6.84 (1H, s), 6.88 (1H, d, J = 2.8 Hz), 7.01 (1H, d, J = 3.2 Hz), 7.60
(4H, m); 13C NMR (CDCl3; 100 MHz) δ 56.0, 56.6, 90.5, 91.8, 111.5,
112.0, 112.3, 116.9, 118.4, 118.8, 128.6, 132.2, 132.3, 133.2, 153.5, 154.9;
ESI-TOF-MS m/z 264 [M þ H]þ; HRMS calcd for C17H14NO2 ([M þ
H]þ) 264.1024, found 264.1030.
Synthesis of 4-(2-(9-bromoanthracen-10-yl)ethynyl)-N,N-
dimethylbenzenamine9c (6B): Using the general procedure, start-
ing from 0.060 g (0.1785 mmol) of 9,10-dibromoanthracene 6 and
0.0258 g (0.1785 mmol) of 4-ethynyl-N,N-dimethylbenzenamine B,
0.016 g (0.0476 mmol) of 9,10-dibromoanthracene was isolated as
unreacted and 0.0305 g (0.0763 mmol) of the title compound was isolated
as a yellow solid. Yield 68%; mp 234-236 °C (reported 236 °C);9c IR
(KBr) 2924, 2854, 2192, 1634, 1605, 1520, 1348, 1188, 811, 752 cm-1; 1H
NMR (CDCl3; 400 MHz) δ 3.03 (6H, s), 6.73 (2H, d, J = 8.4 Hz), 7.56-
7.64 (6H, m), 8.53 (2H, d, J = 8.0 Hz), 8.70 (2H, d, J = 8.8 Hz); 13C NMR
(CDCl3; 100 MHz) δ 40.5, 84.5, 96.2, 103.8, 112.3, 123.0, 126.6, 127.3,
127.6, 127.8, 128.3, 130.6, 132.9, 133.1, 152.8; ESI-TOF-MS m/z 401, 403
[M þ H]þ; HRMS calcd for C24H19BrN ([M þ H]þ) 400.0701, found
400.0697.
Synthesis of 4-(2-(2,5-dimethoxyphenyl)ethynyl)-N,N-di-
methylbenzenamine (4B): Using the general procedure, starting
from 0.050 g (0.2304 mmol) of 2-bromo-1,4-dimethoxybenzene 4 and
0.0367 g (0.2534 mmol) of 4-ethynyl-N,N-dimethylbenzenamine B,
0.046 g (0.1637 mmol) of the title compound was isolated as a lime
semisolid. Yield 71%; IR (KBr) 2924, 2853, 2830, 2207, 1603, 1521,
Synthesis of 4-(2-(pyren-1-yl)ethynyl)benzonitrile (7A):
Using the general procedure, starting from 0.055 g (0.1957 mmol) of
1-bromopyrene 7 and 0.0273 g (0.2152 mmol) of 4-ethynylbenzonitrile
A, 0.062 g (0.1896 mmol) of the title compound was isolated as a yellow
solid. Yield 97%; mp 201-203 °C; IR (KBr) 3037, 2229, 2202, 1604,
1512, 1497, 854, 825, 718, cm-1; 1H NMR (CDCl3; 400 MHz) δ 7.65
(2H, d, J = 8.0 Hz), 7.72 (2H, d, J = 8.4 Hz), 8.01-8.04 (2H, m), 8.09-
8.12 (2H, m), 8.16-8.24 (4H, m), 8.56 (1H, d, J = 9.2 Hz); 13C NMR
(CDCl3; 100 MHz) δ 93.4, 93.6, 111.6, 116.7, 118.8, 124.4, 124.7, 124.8,
125.4, 126.2, 126.6, 127.4, 128.6, 128.9, 130.0, 131.2, 131.4, 132.2,
132.3; ESI-TOF-MS m/z 328 [M þ H]þ; HRMS calcd for C25H14N
([M þ H]þ) 328.1126, found 328.1130.
1499, 1356, 1225, 1197, 1042, 821, 712 cm-1 1H NMR (CDCl3;
;
400 MHz) δ 2.97 (6H, s), 3.76 (3H, s), 3.85 (3H, s), 6.66 (2H, d, J = 7.6
Hz), 6.79 (2H, d, J = 1.6 Hz), 7.01 (1H, d, J = 3.6 Hz), 7.42 (2H, d, J = 8.8
Hz); 13C NMR (CDCl3; 100 MHz) δ 41.4, 55.9, 56.7, 83.7, 94.9, 110.5,
111.9, 112.4, 114.2, 115.1, 118.1, 124.5, 124.6, 133.0, 150.3, 153.5, 154.4;
ESI-TOF-MS m/z 282 [M þ H]þ; HRMS calcd for C18H20NO2 ([M þ
H]þ) 282.1494, found 282.1488.
Synthesis of 4-(2-(4-(cyano)phenyl)ethynyl)-1,8-naphtha-
lic anhydride (5A): Using the general procedure, starting from 0.08 g
(0.2888 mmol) of 4-bromo-1,8-naphthalicanhydride 5 and 0.0404 g
(0.3176 mmol) of 4-ethynylbenzonitrile A, 0.061 g (0.1888 mmol)
of the title compound was isolated pure by filtration followed by washing
with water and ethanol as a yellow solid. Yield 65%; mp >312 °C
(it became black); IR (KBr) 2223, 1778, 1758, 1601, 1588, 1043,
Synthesis of N,N-dimethyl-4-(2-(pyren-1-yl)ethynyl)ben-
zenamine9d (7B): Using the general procedure, starting from 0.055 g
(0.1957 mmol) of 1-bromopyrene 7 and 0.0312 g (0.2152 mmol) of
4-ethynyl-N,N-dimethylbenzenamine B, 0.062 g (0.1797 mmol) of the
title compound was isolated as a bright yellow solid. Yield 92%; mp
168-169 °C (reported 169 °C);9d IR (KBr) 3035, 2922, 2853, 2196,
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dx.doi.org/10.1021/jo200005n |J. Org. Chem. 2011, 76, 2332–2337