ACCEPTED MANUSCRIPT
5
S 8.82 %]; νmax (KBr): 2172, 1726 сm-1; δH (400 MHz, DMSO-
2-Amino-1-(4-phenylthiazol-2-yl)-3-ethoxycarbonylindolizine
(4b).
d6) 8.67 (1 Н, d, J 9.2 Hz, Н-3), 7.95-7.87 (3 Н, m, Н-6, HAr),
7.71 (1 Н, s, Hthiazolyl), 7.69-7.60 (1 H, m, H-4), 7.48 (1 H, t, J 7.5
Hz, HAr), 7.42 (2 H, t, J 7.5 Hz, HAr), 6.86-6.76 (1 Н, m, Н-5),
5.27 (2 Н, s, NCH2), 4.14 (2 Н, q, J 7.1 Hz, CH2CH3), 1.1 (3 Н, t,
J 7.1 Hz, CH2CH3); δC (100 MHz, DMSO-d6) 167.7, 167.1,
153.8, 153.1, 142.8, 137.2, 134.9, 129.0, 128.9, 127.9, 126.5,
126.3, 113.3, 109.1, 62.0, 59.6, 57.7, 14.4; m/z (EI, 70 eV) 363
(100%, M+).
Yellow solid, m.p. 139-140 °C (EtOH); [Found: C, 66.1; H, 5.1;
N, 11.6; S 8.8. C20H17N3O2S requires C, 66.10; H, 4.71; N, 11.56;
S 8.82 %]; νmax (KBr): 3485, 3329, 1668 сm-1; δH (200 MHz,
DMSO-d6) 9.37 (1 Н, d, J 6.8 Hz, Н-5), 8.03 (2 H, d, J 7.0 Hz,
HAr), 7.98 (1 Н, s, Hthiazolyl), 7.81 (1 Н, d, J 8.8 Hz, Н-8), 7.52-
7.31 (4 Н, m, H-7, HAr), 7.07 (2 Н, s, NH2), 6.99 (1 Н, t, J 6.8 Hz,
H-6), 4.36 (2 H, q, J 7.1 Hz, CH2CH3), 1.37 (3Н, t, J 7.1 Hz,
CH2CH3); δC (100 MHz, CDCl3) 170.0, 166.4, 162.0, 153.8,
153.4, 134.5, 134.1, 128.7, 128.0, 126.3, 125.8, 125.4, 118.4,
115.0, 111.5, 107.1, 59.6, 14.8; m/z (EI, 70 eV) 363 (100%, M+).
(E)-2-[4-(4-Methoxyphenyl)thiazol-2-yl-2-[1-(2-ethoxy-2-
oxoethyl)pyridin-2(1H)-ylidene]acetonitrile (3c).
Orange solid, m.p. 158-159 °C (EtOH); [Found: C, 64.1; H, 4.7;
N, 10.7; S 8.1. C21H19N3O3S requires C, 64.10; H, 4.87; N, 10.68;
S 8.15 %]; νmax (KBr): 2171, 1747 сm-1; δH ( 400 MHz, DMSO-
d6) 8.65 (1 H, d, J 9.0 Hz, H-3,), 7.88-7.82 (3 H, m, H-6, HAr),
7.65-7.57 (1 H, m, H-4), 7.54 (1 H, s, Hthiazolyl), 6.97 (2 H, d, J 8.7
Hz, HAr), 6.77 (1 H, t, J 6.7 Hz, H-5), 5.26 (2 H, s, NCH2), 4.15
(2 H, q, J 7.1 Hz, CH2CH3), 3.78 (3 H, s, OCH3), 1.19 (3 H, t, J
7.1 Hz, CH2CH3); δC (100 MHz, DMSO-d6) 171.3, 170.4, 162.7,
157.0, 156.3, 146.3, 141.0, 131.2, 131.0, 127.4, 118.5, 118.0,
117.8, 116.9, 110.7, 65.5, 61.2, 58.9, 17.7; m/z (EI, 70 eV) 393
(100%, M+).
2-Amino-1-(4-methoxyphenylthiazol-2-yl)-3-ethoxycarbonyl-
indolizine (4c).
Yellow solid, m.p. 157 °C (EtOH); [Found: C, 64.1; H, 5.0; N,
10.7; S 8.0. C21H19N3O3S requires C, 64.10; H, 4.87; N, 10.68; S
8.15 %]; νmax (KBr): 3464, 3313, 1670 сm-1; δH (200 MHz,
DMSO-d6)9.36 (1 H, d, J 6.7 Hz, H-5), 7.95 (2 H, d, J 8.8 Hz,
HAr), 7.83-7.79 (2 H, m, H-8, Hthiazolyl), 7.44 (1 H, t, J 9.0 Hz, H-
7), 7.10-6.95 (5 H, m, HAr, NH2, H-6), 4.36 (2 H, q, J 7.1 Hz,
CH2CH3), 3.80 (3 H, s, OCH3), 1.37 (3 H, t, J 7.1 Hz, CH2CH3);
δC (100 MHz, CDCl3) 166.5, 160.8, 158.3, 152.3, 144.5, 133.8,
127.4, 126.4, 124.6, 113.8, 112.8, 110.3, 104.2, 100.0, 99.6, 94.3,
58.4, 54.2, 13.6; m/z (EI, 70 eV) 393 (100%, M+).
(E)-2-[4-(4-Chlorophenyl)thiazol-2-yl-2-[1-(2-ethoxy-2-
oxoethyl)pyridin-2(1H)-ylidene]acetonitrile (3d).
Orange solid, m.p. 183-184 °C (EtOH); [Found: C, 60.41; H,
4.11; N, 10.61. C20H16ClN3O2S requires C, 60.37; H, 4.05; N,
10.56 %]; νmax (KBr): 2173, 1740 сm-1; δH (400 MHz, DMSO-d6)
8.65 (1 Н, d, J 9.3 Hz, Н-3), 7.95-7.87 (3 Н, m, Н-6, HAr), 7.78 (1
H, s, Hthiazolyl), 7.64 (1 Н, dd, J 9.3, 6.7 Hz, Н-4), 7.47 (2 H, d, J
8.5 Hz, HAr), 6.82 (1 H, t, J 6.7 Hz, Н-5), 5.27 (2 Н, s, NCH2),
4.15 (2 Н, q, J 7.1 Hz, CH2CH3), 1.19 (3 Н, t, J = 7.1 Hz,
CH2CH3); δC (100 MHz, DMSO-d6) 167.5, 167.2, 152.6, 152.1,
142.6, 137.5, 133.3, 132.1, 128.7, 127.61, 127.57, 123.6, 123.2,
113.4, 109.5, 61.7, 57.4, 13.9; m/z (EI, 70 eV) 397 (100%, M+).
2-Amino-1-(4-chlorophenylthiazol-2-yl)-3-ethoxycarbonyl-
indolizine (4d).
Yellow solid, m.p. 175-176 °C (EtOH); [Found: C, 60.39; H,
4.10; N, 10.59. C20H16ClN3O2S requires C, 60.37; H, 4.05; N,
10.56 %]; νmax (KBr): 3470, 3316, 1673 сm-1; δH (400 MHz,
DMSO-d6) 9.39 (1 H, s, H-5), 8.10-8. 04 (3 H, m, HAr, Hthiazolyl),
7.83 (1 H, d, J 8.9 Hz, H-8,), 7.53 (2 H, d, J 8.5 Hz, HAr), 7.51-
7.44 (1 H, m, H-7), 7.05 (2 H, s, NH2), 7.01 (1H, t, J 6.5 Hz, H-
6), 4.37 (2 H, q, J 7.1 Hz, CH2CH3), 1.38 (3 H, t, J 7.1 Hz,
CH2CH3); δC (100 MHz, CDCl3) 166.4, 162.2, 161.9, 152.6,
135.4, 133.7, 133.0, 128.8, 128.7, 127.5, 125.9, 115.0, 111.6,
107.5, 106.1, 99.7, 59.6, 14.8; m/z (EI, 70 eV) 397 (100%, M+).
(E)-2-[4-(4-Nitrophenyl)thiazol-2-yl-2-[1-(2-ethoxy-2-
oxoethyl)pyridin-2(1H)-ylidene]acetonitrile (3e).
Orange solid, m.p. 221 °C (EtOH); [Found: C, 58.6; H, 4.2; N,
13.6; S 7.8. C20H16N4O4S requires C, 58.81; H, 3.95; N, 13.72; S
7.85 %]; νmax (KBr): 2169, 1727 сm-1; δH (400 MHz, DMSO-d6)
8.70 (1 Н, d, J 9.5 Hz, Н-3), 8.28 (2 Н, d, J 8.9 Hz, , HAr), 8.17 (2
H, d, J 8.9 Hz, , HAr), 8.09 (1 Н, s, Hthiazolyl), 7.96 (1 H, d, J 7.1
Hz, Н-6), 7.74-7.64 (1 H, m, Н-4), 6.88 (1 H, t, J 7.1 Hz, Н-5),
5.29 (2 Н, s, NCH2), 4.16 (2 Н, q, J 7.2 Hz, CH2CH3), 1.19 (3 Н,
t, J 7.2 Hz, CH2CH3); δC (100 MHz, DMSO-d6) 168.1, 167.7,
153.2, 151.6, 146.7, 143.0, 140.9 137.7, 127.4, 127.1, 124.5,
124.3, 113.9, 113.5, 96.0, 62.1, 57.7, 14.3; m/z (EI, 70 eV) 408
(100%, M+).
2-Amino-1-(4-nitrophenylthiazol-2-yl)-3-ethoxycarbonyl-
indolizine (4e).
Brown solid, m.p. 203-204 °C (EtOH); [Found: C, 58.1; H, 3.6;
N, 13.6; S, 7.7. C20H16N4O4S requires C, 58.81; H, 3.95; N,
13.72; S, 7.85]; νmax (KBr): 3499, 3359, 1667 сm-1; δH (400 MHz,
DMSO-d6) 9.38 (1 Н, s, Н-5), 8.38 (1 Н, s, Hthiazolyl), 8.31 (4 H, s,
HAr), 7.85 (1 Н, d, J 8.9 Hz, Н-8), 7.54-7.44 (1 Н, m, H-7), 7.10-
6.95 (3 Н, m, H-6, NH2), 4.38 (2 H, q, J 7.1 Hz, CH2CH3), 1.39
(3 H, t, J 7.1 Hz, CH2CH3); δC (100 MHz, DMSO-d6) 172.5,
161.1, 158.1, 146.6, 139.8, 138.6, 134.8, 128.2, 126.9, 124.1,
120.3, 114.7, 113.2, 112.5, 109.7, 99.5, 59.4, 14.6; m/z (EI, 70
eV) 408 (100%, M+).
2-Amino-1,3-di(ethoxycarbonyl)indolizine (4a).
White solid, m.p. 113 °C (MeOH); [Found: C, 60.9; H, 5.9; N,
10.1. C14H16N2O4 requires C, 60.86; H, 5.84; N, 10.14 %]; νmax
(KBr): 3515, 3387, 1666 сm-1; δH (400 MHz, DMSO-d6) 9.32 (1
Н, s, Н-5), 7.94 (1 Н, d, J 8.8 Hz, Н-8), 7.41 (1 Н, t, J 7.8 Hz, Н-
7), 7.02 (1 Н, t, J 6.4 Hz, Н-6), 6.48 (2 Н, s, NН2), 4.31 (4 Н, dq,
J 14.3, 7.1 Hz, CH2CH3), 1.34 (6 Н, t, J 7.1 Hz, CH2CH3); δC
(100 MHz, CDCl3) 165.6, 165.5, 161.8, 138.7, 128.2, 126.8,
117.3, 112.8, 99.9, 90.3, 59.6, 59.4, 14.7, 14.6; m/z (EI, 70 eV)
276 (73.2, M+), 158 (100%).
2-Amino-1-cyano-3-ethoxycarbonylindolizine (4f).
Colorless solid, m.p. 151 °C (MeOH); [Found: 62.9; H, 4.9; N,
18.3. C12H11N3O2 requires: C, 62.87; H, 4.84; N, 18.33]; νmax
(KBr): 3469, 3343, 2207, 1675 сm-1; δH (200 MHz, DMSO-d6)
9.25 (1 Н, d, J 7.2 Hz, Н-5), 7.48-7.36 (2 Н, m, Н-7, Н-8), 7.06-
6.98 (1 Н, m, Н-6), 6.49 (2 Н, s, NН2), 4.33 (2 H, q, J 7.0 Hz,
CH2CH3), 1.32 (3 H, t, J 7.0 Hz, CH2CH3); δC (100 MHz, CDCl3)
163.7, 161.2, 139.4, 128.7, 126.9, 115.3, 115.0, 113.3, 100.0,
93.1, 60.1, 14.7; m/z (EI, 70 eV) 229 (100%, M+).