Beilstein J. Org. Chem. 2013, 9, 1819–1825.
= 3179 (NH) cm−1; 1H NMR (400 MHz, CDCl3, 25 °C) δ 2.50
(s, 3H, SCH3), 3.85 (t, J = 4.8 Hz, 4H, N(CH2)2), 4.29 (t, J =
4.8 Hz, 4H, O(CH2)2), 4.74 (d, J = 5.6 Hz, 2H, CH2), 7.28–7.37
(m, 5H, ArH), 12.27 (br. s, 1H, NH) ppm; 13C NMR (100 MHz,
CDCl3, 25 °C) δ 14.6 (SCH3), 43.9 (NCH2Bn), 49.3 (broad,
NCH2), 67.2 (OCH2), 127.5, 127.6, 128.6, 137.0 (Ar-C), 141.4
(C-5), 147.3, 160.1 (C-4 and C-6), 177.7 (C-2) ppm; HRMS
(ES): [M + Na]+ calcd for C16H19N5NaO2S, 368.1152; found,
368.1149.
Supporting Information
Supporting Information File 1
Detailed data of all new materials, photos of the
rearrangement process, copies of the NMR spectra of final
compounds 6 and 8.
N4-Benzyl-N6,N6-diethyl-2-methylthio-5-nitrosopyrimidine-
4,6-diamine (6ec): Blue solid; yield 89%; mp 58–60 °C; IR
(KBr): νmax = 3207 (NH) cm−1; 1H NMR (300 MHz, CDCl3,
25 °C) δ 1.34 (t, J = 6.9 Hz, 6H, (CH3)2), 2.52 (s, 3H, SCH3),
3.91 (q, J = 6.9 Hz, 4H, N(CH2)2), 4.74 (d, J = 6 Hz, 2H, CH2),
7.29–7.36 (m, 5H, ArH), 12.57 (br. s, 1H, NH) ppm; 13C NMR
(75 Hz, CDCl3, 25 °C) δ 12.6 (broad, CH3), 13.9 (broad, CH3),
14.4 (SCH3), 43.7 (NCH2Bn), 46.0 (broad, NCH2Me), 47.6
(broad, NCH2Me), 127.4, 127.7, 128.5, 137.3 (Ar-C), 141.5
(C-5), 147.7, 159.4 (C-4 and C-6), 176.8 (C-2) ppm; HRMS
(ES): [M + H]+ calcd for C16H22N5O2S, 348.1489; found,
348.1485.
Acknowledgments
This research was funded by the European Social Fund under
the Global Grant measure (Grant No. VP1-3.1-ŠMM-07-K-01-
002).
References
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N4,N6-Dibenzyl-2-methylthio-5-nitrosopyrimidine-4,6-di-
amine (6ed): Blue solid; yield 48%; mp 117–119 °C; IR (KBr):
νmax = 3335 (NH) cm−1; 1H NMR (400 MHz, CDCl3, 25 °C) δ
2.55 (s, 3H, SCH3), 4.75 (d, J = 6 Hz, 2H, CH2), 4.88 (d, J = 6
Hz, 2H, CH2), 7.28–7.39 (m, 10H, ArH), 8.17 (br. s, 1H, NH),
11.87 (br. s, 1H, NH) ppm; 13C NMR (100 Hz, CDCl3, 25 °C) δ
14.7 (SCH3), 43.6, 44.9 (NCH2Bn), 127.7, 127.8, 127.9, 128.7,
128.8, 136.8, 137.3 (Ar-C), 137.5 (C-5), 146.0, 161.1 (C-4 and
C-6), 181.2 (C-2) ppm; HRMS (ES): [M + Na]+ calcd for
C19H19N5NaOS, 388.1203; found, 388.1206.
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N4-Benzyl-N6-butyl-2-methylthio-5-nitrosopyrimidine-4,6-
diamine (6ee): Blue solid; yield 89%; mp 82–84 °C; IR (KBr):
νmax 3249 (NH) cm−1; NMR spectra contain signals of two
rotamers. 1H NMR (400 MHz, CDCl3, 25 °C) δ = 0.94–0.99
(m, 3H, CH3), 1.37–1.49 (m, 2H, CH2), 1.56–1.72 (m, 2H,
CH2), 2.53 (s, 3H, SCH3), 3.51–3.55 and 3.64–3.69 (2 m, 2H,
NCH2), 4.72 (d, J = 5.6 Hz, 2H, NCH2Bn), 4.84 (d, J = 6 Hz,
2H, NCH2Bn), 7.28–7.38 (m, 5H, ArH), 7.92 and 8.20 (2 br. s,
1H, NH), 11.66 and 11.92 (2 br. s, 1H, NH) ppm; 13C NMR
(100 Hz, CDCl3, 25 °C) δ 13.5, 13.6 (SCH3), 14.51, 14.53
(CH2), 19.8, 19.9 (CH2), 30.8, 31.2 (CH2), 39.2, 40.6
(NCH2Pr), 43.3, 44.6 (NCH2Bn), 127.4, 127.5, 127.6, 127.7,
128.5, 136.7, 137.19 (Ar-C), 137.24, 137.3 (C-5), 145.9, 146.2,
160.9 (C-4 and C-6), 180.7, 180.9 (C-2) ppm; HRMS (ES):
[M + Na]+ calcd for C16H21N5NaOS, 354.1359; found,
354.1365.
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