2120
M. Baranac-Stojanovich et al.
PAPER
1H NMR (DMSO-d6): d = 1.22 (t, J = 7.0 Hz, 3 H, CH3), 4.15 (q,
J = 7.0 Hz, 2 H, CH2O), 5.73 (s, 1 H, =CH), 7.13 (s, 1 H, CHS), 8.24
(t, J = 7.1 Hz, 2 H, m-Py), 8.75 (t, J = 7.7 Hz, 1 H, p-Py), 9.31 (d,
J = 5.4 Hz, 2 H, o-Py), 12.68 (very br s, NH).
13C NMR (DMSO-d6): d = 14.48 (CH3), 60.18 (CH2O), 71.82
(CHS), 92.58 (=CH), 128.72 (m-Py), 145,07 (o-Py), 148.31 (p-Py),
153.77 (C=), 167.32 (COester), 168.61 (COlactam).
HRMS (ESI): m/z calcd for C13H15N2O3S: 279.0798; found:
279.0791.
1-[(Z)-2-(2-Anilino-2-oxoethylidene)-4-oxo-1,3-thiazolidin-5-
yl]-2-methylpyridinium Bromide (8g)
Gray solid; yield: 90%; mp 197–198 °C.
IR (KBr): 3228, 3183, 3126, 3065, 3028, 2980, 2861, 1725, 1665,
1602, 1544, 1309, 1246, 1154, 828, 766, 696 cm–1.
HRMS (ESI): m/z calcd for C12H13N2O3S: 265.0641; found:
265.0641.
1H NMR (DMSO-d6): d = 2.98 (s, 3 H, CH3), 6.16 (s, 1 H, =CH),
7.04 (t, J = 7.3 Hz, 1 H, p-Ph), 7.31 (t, J = 7.6 Hz, 2 H, m-Ph), 7.31
(s, 1 H, CHS), 7.64 (d, J = 8.0 Hz, 2 H, o-Ph), 8.04 (t, J = 6.9 Hz, 1
H, m-Py), 8.17 (d, J = 7.8 Hz, 1 H, m-Py), 8.60 (t, J = 7.4 Hz, 1 H,
p-Py), 9.29 (d, J = 6.4 Hz, 1 H, o-Py), 10.28 (s, 1 H, NHamide), 12.54
(br s, 1 H, NHlactam).
13C NMR (DMSO-d6): d = 20.95 (CH3), 67.30 (CHS), 96.62 (=CH),
119.09 (o-Ph), 123.35 (p-Ph), 126.77 (m-Py), 128.72 (m-Py),
129.03 (m-Ph), 139.48 (C1-Ph), 143.54 (o-Py), 147.27 (p-Py),
148.88 (o-Py with CH3), 157.60 (C=), 165.30 (COamide), 168.72
(COlactam).
1-[(Z)-2-(2-Anilino-2-oxoethylidene)-4-oxo-1,3-thiazolidin-5-
yl]-3-methylpyridinium Bromide (8d)
Pale brown solid; yield: 92%; mp 188–190 °C.
IR (KBr): 3304, 3257, 3143, 3023, 2939, 2860, 1730, 1653, 1614,
1598, 1550, 1314, 1244, 1191, 829, 754, 685 cm–1.
1H NMR (DMSO-d6): d = 2.55 (s, 3 H, CH3), 6.14 (s, 1 H, =CH),
7.00 (s, 1 H, CHS), 7.04 (t, J = 7.2 Hz, 1 H, p-Ph), 7.31 (t, J = 7.9
Hz, 2 H, m-Ph), 7.63 (d, J = 8.0 Hz, 2 H, o-Ph), 8.14 (dd,
J = 6.2, 7.8 Hz, 1 H, m-Py), 8.59 (d, J = 7.8 Hz, 1 H, p-Py), 9.13 (d,
J = 6.2 Hz, 1 H, o-Py), 9.22 (s, 1 H, o-Py, J = 5.8), 10.28 (s, 1 H,
NHamide), 12.55 (v br s, 1 H, NHlactam).
HRMS (ESI): m/z calcd for C17H16N3O2S: 326.0958; found:
326.0956.
13C NMR (DMSO-d6): d = 18.05 (CH3), 71.69 (CHS), 96.54 (=CH),
119.10 (o-Ph), 123.38 (p-Ph), 127.90 (m-Py), 129.05 (m-Ph),
139.48 (C1-Ph), 139.79 (m-Py with CH3), 142.74 (o-Py), 143.68 (o-
Py), 148.53, 148.89 (p-Py and C=), 165.30 (COamide), 168.38 (CO-
lactam).
1-[(Z)-2-(2-Anilino-2-oxoethylidene)-4-oxo-1,3-thiazolidin-5-
yl]-4-methylpyridinium Bromide (8h)
Gray solid; yield: 92%; mp 188–190 °C.
IR (KBr): 3228, 3179, 3018, 2966, 2851, 1739, 1657, 1634, 1592,
1537, 1491, 1432, 1302, 1238, 1145, 817, 750, 694, 634 cm–1.
HRMS (ESI): m/z calcd for C17H16N3O2S: 326.0958; found:
326.0961.
1H NMR (DMSO-d6): d = 2.66 (s, 3 H, CH3), 6.15 (s, 1 H, =CH), 7.
01 (s, 1 H, CHS), 7.03 (t, J = 7.8 Hz, 1 H, p-Ph), 7.30 (t, J = 7.8 Hz,
2 H, m-Ph), 7.63 (d, J = 8.0 Hz, 2 H, o-Ph), 8.06 (t, J = 6.2 Hz, 1 H,
m-Py), 9.14 (d, J = 6.8 Hz, 2 H, o-Py), 10.28 (s, 1 H, NHamide), 12.52
(br s, 1 H, NHlactam).
1-[(Z)-4-Oxo-2-{2-oxo-2-[(2-phenylethyl)amino]ethylidene}-
1,3-thiazolidin-5-yl]-3-methylpyridinium Bromide (8e)
Pale brown solid; yield: 90%; mp 168–170 °C.
IR (KBr): 3253, 3095, 3021, 2937, 2859, 1726, 1645, 1591, 1569,
1506, 1453, 1309, 1247, 1187, 831, 753, 699 cm–1.
13C NMR (DMSO-d6): d = 21.97 (CH3), 71.04 (CHS), 96.60 (=CH),
119.11 (o-Ph), 123.38 (p-Ph), 129.05 (m-Py), 139.52 (m-Py),
143.83 (C1-Ph), 148.88 (o-Py), 162.09 (C=), 162.09 (C4-Py with
CH3), 166.30 (COamide), 168.58 (COlactam).
1H NMR (DMSO-d6): d = 2.54 (s, 3 H, CH3), 2.74 (t, J = 7.1 Hz, 2
H, CH2Ph), NCH2 is shielded, 5.89 (s, 1 H, =CH), 6.94 (s, 1 H,
CHS), 7.18–7.35 (m, 5 H, Ph), 8.12 (dd, J = 6.2, 8.4 Hz, 1 H, m-Py),
8.29 (t, J = 5.6 Hz, 1 H, NHamide), 8.57 (d, J = 8.4 Hz, 1 H, p-Py),
9.09 (d, J = 6.2 Hz, 1 H, o-Py), 9.17 (s, 1 H, o-Py), 12.24 (br s, 1 H,
NHlactam).
13C NMR (DMSO-d6): d = 18.07 (CH3), 35.42 (CH2Ph), 40.37
(NCH2), 71.78 (CHS), 96.38 (=CH), 126.41 (p-Ph), 127.90 (m-Py),
128.63 (o-Ph), 128.90 (m-Ph), 139.70 (C1-Ph), 139.77 (m-Py, with
CH3), 142,67 (o-Py), 143.65 (o-Py), 146.53 (C=), 148.47 (p-Py),
166.46 (COamide), 168.23 (COlactam).
HRMS (ESI): m/z calcd for C17H16N3O2S: 326.0958; found:
326.0951.
1-[(Z)-2-(2-Anilino-2-oxoethylidene)-4-oxo-1,3-thiazolidin-5-
yl]-3-carbamoylpyridinium Bromide (8i)
Gray solid; yield: 75%; mp 153–156 °C.
IR (KBr): 3371, 3320, 3277, 3197, 3078, 1721, 1692, 1662, 1601,
1548, 1316, 1241, 1162, 811, 753, 693 cm–1.
1H NMR (DMSO-d6): d = 6.13 (s, 1 H, =CH), 7.04 (t, J = 7.3 Hz, 1
H, p-Ph), 7.16 (s, 1 H, CHS), 7.30 (t, J = 7.8 Hz, 2 H, m-Ph), 7.62
(d, J = 7.8 Hz, 2 H, o-Ph), 8.21 (br s, 2 H, NH2), 8.35 (dd,
J = 6.2, 7.8 Hz, 1 H, m-Py), 9.08 (d, J = 8.4 Hz, 1 H, p-Py) 9.43 (d,
J = 6.4 Hz, 1 H, o-Py), 9.61 (s, 1 H, o-Py), 10.25 (s, 1 H, NHamide),
12.51 (br s, 1 H, NHlactam).
HRMS (ESI): m/z calcd for C19H20N3O2S: 354.1271; found:
354.1262.
1-[(Z)-2-(2-Ethoxy-2-oxoethylidene)-4-oxo-1,3-thiazolidin-5-
yl]-3-methylpyridinium Bromide (8f)
Dark yellow solid; yield: 74%; mp 141–144 °C.
13C NMR (DMSO-d6): d = 72.06 (CHS), 96.65 (=CH), 119.10 (o-
Ph), 123.42 (p-Ph), 129.05 (m-Ph), 134.09 (m-Py), 136.29 (m-Py),
139.44 (C1-Ph), 144.83 (o-Py), 145.87 (o-Py), 148.24 (p-Py),
151.37 (C=), 162.64 (COamide), 165.26 (COamide), 168.08 (COlactam).
IR (KBr): 3395, 3057, 2984, 2873, 1724, 1678, 1593, 1503, 1474,
1368, 1292, 1152, 802, 704 cm–1.
1H NMR (DMSO-d6): d = 1.22 (t, J = 7.0 Hz, 3 H, CH3CH2), 2.54
(CH3-Py), 4.14 (q, J = 7.0 Hz, 2 H, CH2O), 5.73 (s, 1 H, =CH), 7.05
(s, 1 H, CHS), 8.14 (dd, J = 6.2, 8.4 Hz, 1 H, m-Py), 8.59 (d, J = 8.4
Hz, 1 H, p-Py), 9.12 (d, J = 6.2 Hz, 1 H, o-Py), 9.21 (s, 1 H, o-Py).
HRMS (ESI): m/z calcd for C17H15N4O3S: 355.0859; found:
355.0882.
13C NMR (DMSO-d6): d = 14.48 (CH3CH2), 18.03 (CH3-Py), 60.15
(CH2O), 71.71 (CHS), 92.48 (=CH), 127.86 (m-Py), 139.82 (m-Py,
with CH3), 142.98 (o-Py), 143.70 (o-Py), 148.71 (p-Py), 153.88
(C=), 167.32 (COester), 168.61 (COlactam).
Acknowledgment
We are grateful to the Ministry of Science of the Republic of Serbia
for financial support (Grant No. 142007 to R.M.).
Synthesis 2008, No. 13, 2117–2121 © Thieme Stuttgart · New York