BEGUNOV et al.
1198
distilled off in a vacuum. From the dry residue the
reaction products were extracted with several portions
of hot anhydrous ethanol (150 mL). The combined
extracts were evaporated in a vacuum to obtain the
corresponding reaction products.
8.63 d (1H, H4, J 8 Hz), 8.99 d (1Н, Н6, J 6.1 Hz), 9.10
d (1Н, Н2, J 0.5 Hz). Mass spectrum, m/z (Irel, %): 253
(47.9) [M]+, 250 (100), 237 (50.4), 181 (22.3), 125
(21.5), 75 (14.9), 63 (15.7), 36 (78.5). Found, %: С
54.01; H 4.10; N 9.59. С13H12ClF3N2. Calculated, %: C
54.09; H 4.19; N 9.70. M 288.70.
Yield of compounds 2а, 2b, 2d, and 2e was 96–98
%; overall yield of isomers mixture 2c and 2c' was
98%; from the mixture compound 2c was isolated in
71% yield. Melting points, 1Н NMR and mass spectra,
and elemental analyses of compounds 2а and 2c–2e
are given in [1].
1-(2-Amino-4-cyanophenyl)pyridinium chloride
1
(3d). Yield 0.47 g (81%), mp 145–148°С. Н NMR
spectrum (DMSO-d6, 500 MHz), δ, ppm: 6.29 s (2Н,
NН2), 7.18 d.d (1Н, Н5', J 6.4, 1.7 Hz), 7.42 d (1Н, Н3',
J 1.7 Hz), 7.60 d (1Н, Н6', J 8.2 Hz), 8.33 t (2Н, Н3,5, J
6.7 Hz), 8.79 t (1Н, Н4, J 7.9 Hz), 9.17 d (2Н, Н2,6, J
5.3 Hz). Mass spectrum, m/z (Irel, %): 196 (22) [M]+,
193 (100), 154 (8), 78 (3). Found, %: С 62.10; H 4.24;
N 18.02. С12H10ClN3. Calculated, %: C 62.21; H 4.35;
N 18.14. M 231.68.
2,4-Dimethyl-7-(trifluoromethyl)pyrido[1,2-a]ben-
1
zimidazole (2b). Yield 0.65 g (98%), mp 126–128°С. H
NMR spectrum (DMSO-d6), δ, ppm: 2.32 s (3H, 2-СН3),
2.53 s (3H, 4-СН3), 7.29 s (1H, Н3, J 0.5 Hz), 7.60 d
(1H, Н9, J 1.5, J 8 Hz), 8.13 d (1H, Н6, J 1.5 Hz), 8.38
d (1H, Н8, J 8.5 Hz), 8.77 d (1H, Н1, J 0.5 Hz). Mass
spectrum, m/z (Irel, %): 264 (100) [M]+, 249 (22), 195
(15), 170 (8), 145 (5), 132 (26), 122 (12), 75 (11), 63
(13), 51 (14), 39 (35). Found, %: С 63.51; H 4.01; N
10.42. С14H11F3N2 Calculated, %: C 63.63; H 4.20; N
10.60. M 264.25.
1-[2-Amino-4-(ethoxycarbonyl)phenyl]pyridi-
nium chloride (3e). Yield 0.55 g (79%), mp 224–226°С.
1Н NMR spectrum (DMSO-d6, 500 MHz), δ, ppm:
1.35 t (3H, CH3, J 7.1 Hz), 4.36 q (2H, CH2, J 7.1 Hz),
6.01 s (2Н, NН2), 7.30 d.d (1Н, Н5', J 8.2, 1.7 Hz), 7.51
d (1Н, Н6', J 8.3 Hz), 7.62 d (1Н, Н3', J 1.7 Hz), 8.33 t
(2Н, Н3,5, J 6.7 Hz), 8.79 t (1Н, Н4, J 7.9 Hz), 9.16 d (2Н,
Н2,6, J 5.6 Hz). Mass spectrum, m/z (Irel, %): 243 (15)
[M]+, 240 (100), 213 (26), 195 (86), 167 (22), 36 (9).
Found, %: С 60.22; H 5.21; N 10.07. С14H15ClN2O2.
Calculated, %: C 60.33; H 5.42; N 10.05. M 278.73.
1Н NMR spectra were registered on a spectrometer
Bruker DRX500 SF-500 MHz, solvent DMSO-d6–CCl4,
internal reference TMS. Mass spectra were obtained on
an instrument Finnigan MAT INCOS 50, ionizing elec-
trons energy 70 eV. Elemental composition was measured
on an elemental analyzer CHN (Carlo Erba 1106, Italia).
1-[2-Amino-4-(trifluoromethyl)phenyl]pyridi-
nium chloride (3а). Yield 0.58 g (84%), mp 196–198°С.
1Н NMR spectrum (DMSO-d6, 500 MHz), δ, ppm:
6.22 s (2Н, NН2), 7.06 d.d (1Н, Н5', J 8.3, 1.4 Hz),
7.35 d (1Н, Н3', J 1.0 Hz), 7.60 d (1Н, Н6', J 8.2 Hz),
8.33 t (2Н, Н3,5, J 7.6 Hz), 8.79 m (1Н, Н4), 9.18 d
(2Н, Н2,6, J 5.5 Hz). Mass spectrum, m/z (Irel, %): 239
(100) [M]+, 170 (18), 78 (15.2), 39 (22). Found, %: С
52.08; H 3.34; N 10.19. С12H10ClF3N2. Calculated, %:
C 52.46; H 3.64; N 10.2. M 274.67.
1-[2-Amino-4-(trifluoromethyl)phenyl]-3,5-dime-
thylpyridinium chloride (3b). Yield 0.70 g (92%), mp
232–234°С. 1Н NMR spectrum (DMSO-d6, 500 MHz),
δ, ppm: 2.51 s (6H, 2CH3), 6.27 s (2H, NH2), 7.03 d.d
(1H, H5', J 8.3, 1.3 Hz), 7.37 d (1H, Н3', J 1.1 Hz),
7.57 d (1H, Н6', J 8.3 Hz), 8.50 s (1H, H4), 8.91 s (2H,
H2,6). Mass spectrum, m/z (Irel, %): 267 [M]+ (28), 265
(100), 251 (27), 195 (6), 132 (7), 108 (4), 77 (7), 39
(7). Found, %: С 55.28; H 4.59; N 9.19. С14H14ClF3N2.
Calculated, %: C 55.55; H 4.66; N 9.25. M 302.72.
The study was carried out under the financial
support of the Ministry of Education and Science of
the Russian Federation (project no. 178 in the frame of
the basic part of the State Contract with NIR of
Yaroslavl State University).
REFERENCES
1. Begunov, R.S., Sokolov, A.A., and Shebunina, T.V.,
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1-[2-Amino-4-(trifluoromethyl)phenyl]-3-me-
thylpyridinium chloride (3c). Yield 0.65 g (90%), mp
190–192°С. 1Н NMR spectrum (DMSO-d6, 500 MHz),
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(1Н, Н5', J 8.3, J 1.5 Hz), 7.33 d (1Н, Н3', J 1.4 Hz),
7.59 d (1Н, Н6', J 8.2 Hz), 8.22 m (1Н, Н5, J 8 Hz),
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 8 2015