SYNTHESIS OF DEUTERIUM LABELED PHENETHYLAMINE DERIVATIVES 1197
2,5-[2H6]-dimethoxy-4-(n-propyl-thio)benzaldehyde (12b), (1.26 g, 5.1 mmol).
1
Yield: 86%. m.p.: 82–838C. H NMR (300 MHz, CDCl3, d): 10.35 (s, 1 H),
7.24 (s, 1 H), 6.76 (s, 1 H), 2.96 (t, J=7.2 Hz, 2 H), 1.82–1.75 (m, 2 H), 1.12
(t, J=7.4 Hz, 3 H). 13C NMR (75 MHz, CDCl3, d): 188.6, 156.9, 150.1, 137.8,
121.3, 110.4, 107.3, 56.0–55.2 (m), 32.9, 21.7, 13.6. IR (KBr): 3037, 3035, 2964,
2927, 2859, 2221, 2069, 1670, 1589, 1481, 1405, 1267, 1226 cmÀ1. MS-FAB
(m/z): 247 (M++1, 100), 246 (38), 133 (10), 75 (6), 43 (4). HRMS-FAB: [M+]
calculated for C12H10D6 O2S, 246.1191; found 246.1195.
Synthesis of 1-ethylsulfanyl-2,5-[2H6]-dimethoxy-4-(2-nitrovinyl)benzene
(13a). Anhydrous ammonium acetate (92 mg) was added to a solution of 2,5-
[2H6]-dimethoxy-4-(ethylthio)benzaldehyde (12a), (2.80 g, 12.0 mmol) in ni-
tromethane (22.9 ml, 420.0 mmol), and the mixture was heated under reflux for
80 min (the reaction progress must be monitored by thin layer chromato-
graphy (TLC), to determine the point at which the starting aldehyde has been
consumed). Excess nitromethane was removed under vacuum leaving an
orange–red crystal of 1-ethylsulfanyl-2,5-[2H6]-dimethoxy-4-(2-nitrovinyl)ben-
zene (13a), (3.15 g, 11.4 mmol). Yield: 95%. m.p.: 153–1548C. 1H NMR
(300 MHz, CDCl3, d): 8.14 (d, J=13.5 Hz, 1 H), 7.86 (d, J=13.5 Hz, 1 H),
6.82 (s, 1 H), 6.76 (s, 1 H), 3.03 (q, J=7.4 Hz, 2 H), 1.42 (t, J=7.4 Hz, 3 H).
13C NMR (75 MHz, CDCl3, d): 154.3, 150.2, 137.1, 135.2, 134.3, 115.4,
112.1, 109.5, 56.1–55.0 (m), 25.3, 13.5. IR (KBr, thin film): 3097, 2975,
2931, 2227, 2069, 1612, 1594, 1490, 1413, 1342, 1247, 1226 cmÀ1. MS-FAB
(m/z): 276 (M++1, 3), 257 (2), 247 (2), 217 (7), 215 (3), 75 (1 0 0), 74
(17). HRMS-FAB (m/z): [M+] calculated for C12H9D6NO4S, 275.1092;
found 275.1104.
Synthesis of 1,4-[2H6]-dimethoxy-2-(2-nitrovinyl)-5-propylsulfanylbenzene
(13b). Anhydrous ammonium acetate (39 mg) was added to a solution of
2,5-[2H6]-dimethoxy-(n-propylthio)benzaldehyde (12b), (1.26 g, 5.1 mmol) in
nitromethane (9.79 ml, 180.0 mmol, and the mixture was heated under
reflux for 1 h (this reaction progress must be monitored by TLC, to determine
the point at which the starting aldehyde has been consumed). Excess
nitromethane was removed under vacuum leaving an orange–red crystal of
1,4-[2H6]-dimethoxy-2-(2-nitrovinyl)-5-propylsulfanylbenzene (13b), (1.41 g,
1
4.9 mmol). Yield: 95%. m.p.: 121–1228C. H NMR (300 MHz, CDCl3, d):
8.14 (d, J=13.5 Hz, 1 H), 7.85 (d, J=13.6 Hz, 1 H), 6.82 (s, 1 H), 6.76 (s, 1 H),
2.96 (t, J=7.2 Hz, 1 H), 1.83–1.71 (m, 2 H), 1.11 (t, J=7.3 Hz, 3 H). 13C NMR
(75 MHz, CDCl3, d): 154.3, 150.2, 136.9, 135.2, 134.6, 115.3, 112.0, 109.3,
56.1–54.7 (m), 33.1, 21.9, 13.6. IR (KBr, thin film): 3142, 2967, 2940, 2070,
1616, 1602, 1553, 1490, 1387, 1342, 1275, 1239, 1100 cmÀ1. MS-FAB (m/z):
290 (M++1, 46), 289 (12), 274 (46), 260 (8), 246 (19), 244 (1 0 0), 218 (12), 43
Copyright # 2006 John Wiley & Sons, Ltd.
J Label Compd Radiopharm 2006; 49: 1187–1200
DOI: 10.1002/jlcr