806
V. V. Kouznetsov et al. / Bioorg. Med. Chem. 16 (2008) 794–809
J = 6.4 Hz, 4-H), 4.15 (1H, br s, NH), 2.60 (2H, q,
J = 6.9 Hz, –CH2), 2.23 (3H, s, CH3); 13C NMR
(CDCl3, 75 MHz): d 145.0, 134.5 (+), 129.6 (2C, +),
126.7, 126.1 (+), 125.9 (+), 120.7 (+), 118.2 (À), 117.6,
113.6 (2C, +), 53.6 (+), 41.9 (À), 20.3 (+). MS m/z
(EI) 243 (M+), 202 [(M–C3H5)+]. Found: C, 74.34; H,
7.32; N, 5.43; calcd for C15H17NS: C, 74.03; H, 7.04;
N, 5.76.
1.5 Hz, 2(6)-HPy), 7.29 (2H, d, J = 6.0 Hz, 3(5)-HPy),
6.68 (2H, d, J = 8.9 Hz, 3(5)-HAr), 6.40 (2H, d,
J = 8.9 Hz, 2(6)-HAr), 5.77–5.67 (1H, m, @CH), 5.20
(1H, d, J = 6.0 Hz, CH2A@), 5.16 (1H, s, CH2B@),
4.29 (1H, dd, J = 8.0, 5.0 Hz, 4-H), 4.20 (1H, br s,
NH), 3.68 (3H, s, OCH3), 2.61–2.41 (2H, m, CH2); 13C
NMR (CDCl3, 100 MHz): d 153.1, 152.2 149.8 (2C,
+), 140.8, 133.6 (+), 121.6 (2C, +), 119.0 (À), 114.7
(2C, +), 114.5 (2C, +), 57.0 (+), 55.6 (+), 42.4 (À). MS
m/z (EI) 254 (M+), 213 [(M–C3H5)+]. Found: C, 75.29;
H, 7.32; N, 11.12; calcd for C16H18N2O: C, 75.56; H,
7.13; N, 11.01.
4.1.2.7. N-[1-(Thien-3-yl)but-3-enyl]-N-(4-chlorophenyl)-
amine (89). Yellow oil. Yield 48%. IR (film): m 3413,
1597 (s, NH), 1497, 922 cmÀ1 (s, C@CH); 1H NMR
(CDCl3, 300 MHz): d 7.29 (1H, dd, J = 4.9, 3.0 Hz, 5-
HThie), 7.12 (1H, br d, J = 2.9 Hz, 2-HThie), 7.06 (2H,
d, J = 8.8 Hz, 3(5)-HAr), 7.04 (1H, dd, J = 5.3, 1.0 Hz,
4-HThie), 6.48 (2H, d, J = 8.7 Hz, 2(6)-HAr), 5.84–5.65
(1H, m, @CH), 5.21–5.14 (2H, m, CH2@), 4.50 (1H, t,
J = 6.5 Hz, 4-H), 4.18 (1H, br s, NH), 2.69–2.52 (2H,
m, –CH2); 13C NMR (CDCl3, 75 MHz): d 145.7,
144.2, 134.1 (+), 128.9 (2C, +), 126.2 (+), 125.9 (+),
122.2, 120.9 (+), 118.5 (À), 114.6 (2C, +), 53.5 (+),
41.8 (À). MS m/z (EI) 263 (M+), 222 [(M–C3H5)+ for
35Cl]. Found: C, 63.56; H, 5.07; N, 5.15; calcd for
C14H14ClNS: C, 63.74; H, 5.35; N, 5.31.
4.1.2.11. N-(4-Bromophenyl)-N-[1-(pyridin-4-yl)but-3-
enyl]amine (93). Yellow oil. Yield 75%. IR (film): m 3410,
1593 (s, NH), 1493, 922 cmÀ1 (s, C@CH); 1H NMR
(CDCl3, 300 MHz): d 8.55 (2H, dd, J = 4.4, 1.6 Hz,
2(6)-HPy), 7.27 (2H, dd, J = 3.9, 1.7 Hz, 3(5)-HPy), 7.16
(2H, dd, J = 8.8, 2.0 Hz, 3(5)-HAr), 6.31 (2H, dd,
J = 8.8, 2.0 Hz, 2(6)-HAr), 5.78–5.63 (1H, m, @CH),
5.23–5.17 (2H, m, CH2@), 4.34 (1H, quintet,
J = 4.1 Hz, 4-H), 4.19 (1H, br s, H–N), 2.67–2.58 (1H,
m, –CHA), 2.52–2.42 (1H, m, –CHB); 13C NMR (CDCl3,
75 MHz): d 150.1 (+), 150.0 (+), 145.5, 133.2 (+), 131.9
(2C, +), 128.1, 121.5 (2C, +), 119.5 (À), 115.0 (2C, +),
109.7, 56.2 (+), 42.3 (À). MS m/z (EI) 302 (M+), 263
[(M–C3H5)+ for 81Br]. Found: C, 59.66; H, 5.16;
N, 9.45; calcd for C15H15BrN2: C, 59.42; H, 4.99; N,
9.24.
4.1.2.8. N-[1-(1-Methyl-1H-pyrrol-2-yl)but-3-enyl]-N-
(4-chlorophenyl)amine (90). Yellow oil. Yield 45%. IR
(film): m 3413, 1601 (s, NH), 1500, 918 cmÀ1 (s, C@CH);
1H NMR (CDCl3, 300 MHz): d 7.13 (1H, t, J = 2.7 Hz,
5-HPyr), 7.10 (2H, dd, J = 8.2, 2.5 Hz, 3(5)-HAr), 6.62
(1H, br s, 4-HPyr), 6.59 (1H, br s, 3-HPyr), 6.54 (2H,
dd, J = 8.8, 2(6)-HAr), 6.01–5.75 (1H, m, @CH),
5.31–5.13 (2H, m, CH2@), 4.05 (1H, br s, NH), 3.75
(1H, dt, J = 5.3, 1.6 Hz, 4-H), 3.57 (3H, s, CH3–N),
2.66 (2H, t, J = 6.8 Hz, –CH2); 13C NMR (CDCl3,
75 MHz): d 146.5, 134.9, 133.5 (+), 129.0 (2C, +),
116.4, 116.2 (À), 114.0 (2C, +), 113.5 (+), 106.7 (+),
106.6 (+), 52.9 (+), 46.6 (À), 33.9 (+). MS m/z (EI)
260 (M+), 219 [(M–C3H5)+ for 35Cl]. Found: C,
69.34; H, 6.90; N, 10.66; calcd for C15H17ClN2: C,
69.09; H, 6.57; N, 10.74.
4.1.2.12. N-(3,5-Dimethylphenyl)-N-[1-(pyridin-4-yl)-
but-3-enyl]amine (94). Yellow oil. Yield 85%. IR: m
3494, 1605 (s, NH), 1500, 914 cmÀ1 (s, C@CH); 1H
NMR (CDCl3, 400 MHz): d 8.54 (2H, dd, J = 4.5,
1.5 Hz, 2(6)-HPy), 7.29 (2H, dd, J = 4.7, 1.3 Hz, 3(5)-
HPy), 6.34 (1H, s, 4-HAr), 6.08 (2H, s, 2(6)-HAr),
5.76–5.65 (1H, m, @CH), 5.20–5.15 (2H, m, CH2@),
4.35 (1H, dd, J = 7.7, 5.0 Hz, 4-H), 4.07 (1H, br s,
H–N), 2.62–2.55 (1H, m, –CHA), 2.48–2.41 (1H, m,
–CHB), 2.15 (6H, s, 3(5) –CH3); 13C NMR (CDCl3,
100 MHz): d 152.9, 150.0 (2C, +), 146.8, 138.8 (2C),
133.6 (+), 121.5 (2C, +), 119.9 (+), 119.0 (À), 111.3
(2C, +), 56.2 (+), 42.4 (À), 21.4 (2C, +). MS m/z
(EI) 252 (M+), 211 [(M–C3H5)+]. Found: C, 81.14;
H, 7.70; N, 11.21; calcd for C17H20N2: C, 80.91; H,
7.99; N, 11.10.
4.1.2.9. N-(4-Phenyl)-N-[1-(pyridin-4-yl)but-3-enyl]-
amine (91). Yellow oil. Yield 80%. IR (film): m 3406,
1601 (s, NH), 1504, 922 cmÀ1 (s, C@CH); 1H NMR
(CDCl3, 400 MHz): d 8.56 (2H, dd, J = 5.0, 1.6 Hz,
2(6)-HPy), 7.31 (2H, dd, J = 4.4, 1.6 Hz, 3(5)-HPy), 7.10
(2H, td, J = 7.7, 1.0 Hz, 3(5)-HPh), 6.69 (1H, tt,
J = 7.3, 1.9 Hz, 4-HPh), 6.45 (2H, d, J = 8.5 Hz, 2(6)-
HPh), 5.80–5.66 (1H, m, @CH), 5.24–5.18 (2H, m,
CH2@), 4.38 (1H, dd, J = 7.9, 5.0 Hz, 4-H), 4.19 (1H,
br s, H–N), 2.66–2.57 (1H, m, –CHA), 2.53–2.43 (1H,
m, –CHB); 13C NMR (CDCl3, 100 MHz): d 152.8,
150.0 (2C, +), 146.6, 133.5 (+), 129.1 (2C, +), 121.6
(2C, +), 119.1 (À), 117.9 (+), 113.4 (2C, +), 56.2 (+),
42.4 (À). MS m/z (EI) 224 (M+), 183 [(M–C3H5)+].
Found: C, 80.54; H, 7.04; N, 12.40; calcd for
C15H16N2: C, 80.32; H, 7.19; N, 12.49.
4.1.3. Type C. New a-aminonitriles were obtained
following the procedures described by De et al.17
4.1.3.1. 2-(2-Furyl)-2-(phenylamino)acetonitrile (95).
Yellow oil. Yield 61%. IR (film): m 3359, 1605 (s, NH),
2241 cmÀ1 (s, CN); 1H NMR (CDCl3, 300 MHz): d
7.41 (1H, t, J = 0.9 Hz, 5-HFu), 7.19 (2H, d,
J = 7.5 Hz, 3(5)-HPh), 6.85 (1H, td, J = 7.4, 0.9 Hz, 4-
HPh), 6.71 (2H, dd, J = 7.7, 0.8 Hz, 2(6)-HPh), 6.52
(1H, dd, J = 3.3, 0.7 Hz, 4-HFu), 6.36 (1H, dd, J = 3.1,
1.8 Hz, 3-HFu), 5.41 (1H, s, HC–CN), 4.11 (1H, br s,
H–N); 13C NMR (CDCl3, 75 MHz): d 146.0, 144.1,
144.0 (+), 129.6 (2C, +), 120.7 (+), 116.4, 114.5 (2C,
+), 110.9 (+), 109.6 (+), 44.4 (+). MS m/z (EI) 198
(M+). Found: C, 72.85; H, 5.23; N, 14.25; calcd for
C12H10N2O: C, 72.71; H, 5.08; N, 14.13.
4.1.2.10. N-(4-Methoxylphenyl)-N-[1-(pyridin-4-yl)-
but-3-enyl]amine (92). Yellow oil. Yield 85%, IR (film):
1
m 3309, 1597 (s, NH), 1512, 922 cmÀ1 (s, C@CH); H
NMR (CDCl3, 400 MHz): d 8.53 (2H, dd, J = 4.5,