A SIMPLE APPROACH TO THE SYNTHESIS
Spectral characteristics of compounds I and III
527
Comp. no.
m/z (Irel, %)
214 (43), 186 (26), 137 (30), 13.84 s (0.3H, NH), 13.72 s (0.7H, NH), 11.75 s (0.7H, NH), 11.68 (0.3H, NH), 7.81–7.46
105 (100), 77 (75), 70 (21)
m (5Н, СНarom), 7.70–7.68 m (1Н, С5Н), 5.78–5.71 m (2Н, СН)
228 (39), 200 (18), 151 (37), 14.40 s (0.5Н, NH), 13.70 s (0.5Н, NH), 11.74 s (0.5Н, NH), 11.54 s (0.5Н, NH), 7.65–7.47
1H NMR spectrum (DMSO-d6), δ, ppm (J, Hz)
Iа
Ib
Ic
105 (100), 84 (32), 77 (90)
m (5Н, СНarom), 5.80 s (0.5Н, СН), 5.72 s (0.5Н, СН), 5.66 s (0.5Н, СН), 5.57 s (0.5Н, СН),
2.23 s (1.5Н, СН3), 2.15 s (1.5Н, СН3)
304 (51), 276 (17), 181 (100), 14.44 s (0.5Н, NH), 13.76 s (0.5Н, NH), 11.83 s (0.5Н, NH), 11.60 s (0.5Н, NH), 7.90–7.40
152 (34), 84 (22)
m (9Н, СНarom), 5.86 s (0.5Н, СН), 5.78 s (0.5Н, СН), 5.68 s (0.5Н, СН), 5.60 s (0.5Н, СН),
2.25 s (1.5Н, СН3), 2.17 s (1.5Н, СН3)
246 (57), 218 (7) 137 (100),
109 (22)
13.79 s (1Н, NH), 11.55 s (1Н, NH), 9.47 s (1Н, ОH), 9.20 s (1Н, ОH), 7.62 m (1Н, С6Н),
7.25 m (3Н, СНarom), 5.62 m (2Н, СН)
Id
Ie
260 (80), 232 (6), 151 (23),
14.46 s (0.5Н, NH), 13.67 s (0.5Н, NH), 11.56 s (0.5Н, NH), 11.31 s (0.5Н, NH), 9.46 s
137 (100), 124 (34), 109 (19), (1Н, ОH), 9.18 s (1Н, ОH), 7.26–6.77 m (3Н, СНarom), 5.66 s (0.5Н, СН), 5.60 s (0.5Н,
84 (21) СН), 5.58 s (0.5Н, СН), 5.48 s (0.5Н, СН), 2.20 s (1.5Н, СН3), 2.12 s (1.5Н, СН3)
272 (27), 244 (13), 163 (100) 13.74 s (0.3Н, NH), 13.64 s (0.7Н, NH), 11.62 s (1Н, NH), 7.67 d (1Н, С6Н, J 6.0), 6.28–
6.19 m (3Н, СНarom), 5.67 m (2Н, СН,), 4.28 s (4Н, СН2)
If
286 (35), 258 (7), 163 (100), 14.33 s (0.5Н, NH), 13.63 s (0.5Н, NH), 11.60 s (0.5Н, NH), 11.35 s (0.5Н, NH), 7.26–6.91
151 (10), 135 (12), 107 (11), m (3Н, СНarom) 5.67 s (0.5Н, СН), 5.66 s (0.5Н, СН), 5.58 s (0.5Н, СН), 5.57 s (0.5Н, СН),
Ig
84 (9)
4.28 s (4Н, СН2), 2.18 s (1.5Н, СН3), 2.14 s (1.5Н, СН3)
270 (30), 269 (100), 200 (7)
11.57 s (1Н, NH), 7.92 br.s (1Н, С6Н), 7.63 s (2H, NH2), 7.49–7.38 m (5Н, СНarom), 6.16
br.s (1Н, С5Н, J 4.8)
IIIа
IIIb
IIIc
IIId
IIIe
IIIf
IIIg
284 (78), 283 (100), 200 (18) 11.28 s (1Н, NH), 7.53 s (2H, NH2), 7.51–7.38 m (5Н, СНarom), 5.99 s (1Н, С5Н), 2.16 s
(3H, CH3)
360 (27), 359 (100), 276 (10) 11.78 s (1Н, NH), 7.73–7.37 m (9H, СНarom), 7.67 s (2H, NH2), 6.07 s (1Н, С5Н), 2.19 s
(3H, CH3)
302 (76), 301 (100,) 232 (7)
11.00 s (1Н, NH), 9.26 s (1Н, ОH), 9.14 s (1Н, ОH), 7.87 d (1Н, С6Н, J 6.0), 7.63 s (2H,
NH2), 6.93 s (1Н, СНarom), 6.74 s (2Н, СНarom), 6.10 d (1Н, С5Н, J 6.0)
316 (100), 315 (10), 232 (10) 10.83 s (1Н, NH), 9.24 s (1Н, ОH), 9.15 s (1Н, ОH), 7.59 s (2H, NH2), 6.93 s (1Н, СНarom),
6.74 s (2Н, СНarom), 5.96 s (1Н, С5Н), 2,15 s (3H, CH3)
328 (54), 327 (100), 258 (1)
11.57 s (1Н, NH), 7.93 d (1Н, С6Н, J 6.0), 7.60 s (2H, NH2), 6.98–6.83 m (3Н, СНarom),
6.17 d (1Н, С5Н, J 6.0), 4.26 s (4Н, СН2)
11.50 s (1Н, NH), 7.61 s (2H, NH2),7.00–6.84 m (3Н, СНarom), 6.03 s (1Н, С5Н),4.27 s (4Н,
342 (100), 341 (57), 258 (6)
2СН2), 2.17 s (3H, CH3)
If, there is the predominance of one of the isomers (see
the table). The mass spectra of pyrimidines Iа–Ig contain
the peaks of the molecular ions of medium intensity,
whose primary fragmentation consists in a concurrent
cleavage of the aryl moiety and the carbonyl group. In
addition, there are intensive peaks of ArCO+ cations.
thiourea in ethanol. The structure of the reaction
products was proved by the mass spectrometry and 1H
NMR spectroscopy (see the table). The mass spectra of
thiazoles IIIа–IIIg contain the intensive peaks of the
molecular ions. The main direction of their
fragmentation is due to the loss of the hydrogen atom
and the pyrimidine ring decay to eliminate the
1
4,5-Disubstituted 2-aminothiazoles IIIа–IIIg were
synthesized by the Hantzsch–Traumann reaction [7, 8]
of pyrimidines Iа–Ig with an equimolar amount of
bromine, followed by heating with an excess of
RC2HCONH fragment. In the H NMR spectra of
compounds IIIа–IIIg there are the signals of amide
proton at 11.78–10.83 ppm, two amino protons at
7.67–7.53 ppm, the H5,6 proton of pyrimidine ring
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 3 2013