Chemistry of Heterocyclic Compounds 2019, 55(3), 235–239
−63.94. Found, %: C 69.13; H 4.42; N 7.30. C22H17F3N2O.
2JCF = 31.0, C–CF3); 180.0 (C=O). 19F NMR spectrum, δ, ppm:
−68.63. Found, %: C 69.70; H 4.80; N 7.02. C23H19F3N2O.
Calculated, %: C 69.69; H 4.83; N 7.07.
Calculated, %: C 69.10; H 4.48; N 7.33.
3-[(4-Bromophenyl)imino]-4,4,4-trifluoro-1-oxo-1-phenyl-
2-(pyridinium-1-yl)butan-2-ide (4d) was synthesized from
pyridine 1a, phenacyl bromide 2a, and imidoyl chloride 3d.
Yield 438 mg (98%), orange solid, mp >300°C. IR spectrum,
3-[(2-Chlorophenyl)imino]-4,4,4-trifluoro-2-(4-methyl-
pyridinium-1-yl)-1-oxo-1-phenylbutan-2-ide (4h) was synthe-
sized from pyridine 1b, phenacyl bromide 2a, and imidoyl
chloride 3f. Yield 396 mg (95%), red solid, mp >300°C.
IR spectrum, ν, cm–1: 1627 (C=O), 1592 (C=N). 1H NMR
spectrum, δ, ppm (J, Hz): 2.44 (3H, s, CH3); 6.78–6.90
(1H, m, H Ar); 6.97−7.03 (3H, m, H Ar); 7.25−7.30 (5H,
m, H Ar); 7.55 (2H, br. s, H Py); 8.47 (2H, br. s, H Py).
13C NMR spectrum, δ, ppm (J, Hz): 21.5 (CH3); 120.5;
1
ν, cm–1: 1632 (C=O), 1585 (C=N). H NMR spectrum,
δ, ppm (J, Hz): 6.51 (2H, d, 3JHH = 8.0, H Ar); 7.11 (2H, d,
3JHH = 8.0, H Ar); 7.16−7.20 (2H, m, H Ar); 7.24 (2H, t,
3JHH = 8.0, H Ar); 7.30−7.34 (1H, m, H Ar); 7.84 (2H, br. s,
H Py); 8.29 (1H, m, H Py); 8.75 (2H, br. s, H Py).
13C NMR spectrum, δ, ppm (J, Hz): 115.1; 121.6 (q,
1JCF = 289.1, CF3); 122.1; 127.7; 127.8; 128.2; 129.9;
1
121.3 (q, JCF = 280.2, CF3); 124.1; 125.7; 127.5; 127.7;
2
131.7; 141.9; 143.2; 148.9; 149.5; 152.5 (q, JCF = 32.0,
127.8; 128.3; 129.7; 129.8; 142.4; 147.1; 148.6; 152.7 (q,
2JCF = 29.0, C–CF3); 156.9; 181.0 (C=O). 19F NMR
spectrum, δ, ppm: −68.53. Found, %: C 63.35; H 3.89; N 6.70.
C22H16ClF3N2O. Calculated, %: C 63.39; H 3.87; N 6.72.
3-[(4-Bromophenyl)imino]-4,4,4-trifluoro-2-(4-methyl-
pyridinium-1-yl)-1-oxo-1-phenylbutan-2-ide (4i) was
synthesized from pyridine 1b, phenacyl bromide 2a, and
imidoyl chloride 3d. Yield 442 mg (96%), orange solid,
mp >300°C. IR spectrum, ν, cm–1: 1603 (C=O), 1580
C–CF3); 180.1 (C=O). 19F NMR spectrum, δ, ppm: −68.10.
Found, %: C 56.43; H 3.12; N 6.20. C21H14BrF3N2O.
Calculated, %: C 56.39; H 3.16; N 6.26.
1-(4-Bromophenyl)-4,4,4-trifluoro-3-[(4-methylphenyl)-
imino]-1-oxo-2-(pyridinium-1-yl)butan-2-ide (4e) was synthe-
sized from pyridine 1a, phenacyl bromide 2b, and imidoyl
chloride 3c. Yield 438 mg (95%), orange solid, mp >300°C.
1
IR spectrum, ν, cm–1: 1686 (C=O), 1587 (C=N). H NMR
1
spectrum, δ, ppm (J, Hz): 2.13 (3H, s, CH3); 6.47 (2H, d,
(C=N). H NMR spectrum, δ, ppm (J, Hz): 2.52 (3H, s,
3
3JHH = 8.0, H Ar); 6.77 (2H, d, 3JHH = 8.0, H Ar); 7.06 (2H,
CH3); 6.49 (2H, d, JHH = 8.0, H Ar); 7.09−7.13 (4H, m,
3
3
d, JHH = 8.0, H Ar); 7.40 (2H, d, JHH = 8.0, H Ar); 7.79
(2H, br. s, H Py); 8.24 (1H, br. s, H Py); 8.67 (2H, br. s,
H Py). 13C NMR spectrum, δ, ppm (J, Hz): 20.9 (CH3);
H Ar); 7.17−7.25 (2H, m, H Ar); 7.28−7.32 (1H, m, H Ar);
3
7.70 (2H, br. s, H Py); 8.62 (2H, d, J = 8.0, H Py).
13C NMR spectrum, δ, ppm (J, Hz): 21.6 (CH3); 114.8;
1
1
110.0; 119.8; 121.5 (q, JCF = 278.7, CF3); 122.9; 127.5;
121.7 (q, JCF = 281.0, CF3); 122.1; 127.7; 128.0; 128.2;
2
129.4; 129.7; 131.1; 132.7; 142.6; 146.8; 147.2; 148.2;
129.7; 131.6; 142.0; 148.4; 149.8; 152.0 (q, JCF = 35.0,
152.5 (q, JCF = 30.0, C–CF3); 177.3 (C=O). 19F NMR
C–CF3); 156.9; 180.2 (C=O). 19F NMR spectrum, δ, ppm:
2
spectrum, δ, ppm: −61.19. Found, %: C 57.31; H 3.55; N 6.01.
C22H16BrF3N2O. Calculated, %: C 57.28; H 3.50; N 6.07.
1-(4-Bromophenyl)-4,4,4-trifluoro-3-[(4-methoxyphenyl)-
imino]-1-oxo-2-(pyridinium-1-yl)butan-2-ide (4f) was synthe-
sized from pyridine 1a, phenacyl bromide 2b, and imidoyl
chloride 3e. Yield 448 mg (94%), red solid, mp >300°C.
IR spectrum, ν, cm–1: 1687 (C=O), 1628 (C=N). 1H NMR
spectrum, δ, ppm (J, Hz): 3.67 (3H, s, OCH3); 6.55−6.62
(4H, m, H Ar); 7.10 (2H, d, 3JHH = 8.0, H Ar); 7.43 (2H, d,
3JHH = 8.0, H Ar); 7.84 (2H, br. s, H Py); 8.26 (1H, br. s,
H Py); 8.74 (2H, br. s, H Py). 13C NMR spectrum, δ, ppm
−61.00. Found, %:
C
57.23;
H
3.54;
N
6.02.
C22H16BrF3N2O. Calculated, %: C 57.28; H 3.50; N 6.07.
1-(4-Bromophenyl)-3-[(4-chlorophenyl)imino]-4,4,4-
trifluoro-2-(4-methylpyridinium-1-yl)-1-oxobutan-2-ide
(4j) was synthesized from pyridine 1b, phenacyl bromide
2b, and imidoyl chloride 3a. Yield 471 mg (95%), yellow
solid, mp >300°C. IR spectrum, ν, cm–1: 1637 (C=O), 1500
1
(C=N). H NMR spectrum, δ, ppm (J, Hz): 2.56 (3H, s,
3
CH3); 6.58 (2H, d, JHH = 8.1, H Ar); 6.99−7.04 (4H, m,
3
H Ar); 7.42 (2H, d, JHH = 8.1, H Ar); 7.74 (2H, br. s,
H Py); 8.66 (2H, br. s, H Py). 13C NMR spectrum, δ, ppm
1
1
(J, Hz): 55.7 (OCH3); 121.4; 121.6 (q, JCF= 280.1, CF3);
(J, Hz): 21.7 (CH3); 115.6 (q, JCF = 279.0, CF3); 121.7;
122.9; 127.6; 128.4; 129.7; 130.7; 131.1; 132.8; 142.7;
123.0; 127.0; 128.1; 128.8; 129.7; 131.2; 141.1; 148.4;
2
2
144.4; 147.9; 151.7 (q, JCF = 31.0, C–CF3); 156.2; 177.3
149.3; 152.0 (q, JCF = 29.0, C–CF3); 157.3; 178.7 (C=O).
(C=O). 19F NMR spectrum, δ, ppm: −73.91. Found, %:
C 55.32; H 3.40; N 5.85. C22H16BrF3N2O2. Calculated, %:
C 55.36; H 3.38; N 5.87.
19F NMR spectrum, δ, ppm: −68.53. Found, %: C 53.28;
H 3.01; N 5.61. C22H15BrClF3N2O. Calculated, %: C 53.30;
H 3.05; N 5.65.
4,4,4-Trifluoro-3-[(4-methylphenyl)imino]-2-(4-methyl-
pyridinium-1-yl)-1-oxo-1-phenylbutan-2-ide (4g) was
synthesized from pyridine 1b, phenacyl bromide 2a, and
imidoyl chloride 3c. Yield 377 mg (95%), yellow solid,
mp >300°C. IR spectrum, ν, cm–1: 1632 (C=O), 1577
1-(4-Bromophenyl)-4,4,4-trifluoro-3-[(4-fluorophenyl)-
imino]-2-(4-methylpyridinium-1-yl)-1-oxobutan-2-ide (4k)
was synthesized from pyridine 1b, phenacyl bromide 2b,
and imidoyl chloride 3g. Yield 460 mg (96%), red solid,
mp >300°C. IR spectrum, ν, cm–1: 1635 (C=O), 1589
1
1
(C=N). H NMR spectrum, δ, ppm (J, Hz): 2.16 (3H, s,
(C=N). H NMR spectrum, δ, ppm (J, Hz): 2.56 (3H, s,
3
CH3); 2.49 (3H, s, CH3); 6.45 (2H, d, JHH = 8.0, H Ar);
CH3); 6.58−6.61 (2H, m, H Ar); 6.79−6.83 (2H, m, H Ar);
3
3
6.77 (2H, d, 3JHH = 8.0, H Ar); 7.17−7.29 (5H, m, H Ar); 7.56
(2H, br. s, H Py); 8.45 (2H, br. s, H Py). 13C NMR
spectrum, δ, ppm (J, Hz): 20.9 (CH3); 21.5 (CH3); 119.9;
7.05 (2H, d, JHH = 8.1, H Ar); 7.42 (2H, d, JHH = 8.1,
H Ar); 7.73 (2H, br. s, H Py); 8.65 (2H, br. s, H Py).
13C NMR spectrum, δ, ppm (J, Hz): 21.6 (CH3); 115.5 (d,
121.4 (q, JCF = 280.1, CF3); 127.8; 128.1; 129.3; 129.4;
2JCF = 22.0, C–CF); 121.5 (d, JCF = 8, C–C–CF); 121.7 (d,
1
3
129.5; 129.9; 132.2; 141.9; 142.6; 147.8; 148.3; 150.6 (q,
1JCF = 280.0, CF3); 123.0; 128.1; 129.7; 131.1; 141.2; 145.6;
238