REACTIVITY STUDY OF 2,4-DINITROBUTA-1,3-DIENES
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4-Chloro-1,1,3-tris(ethylthio)-2,4-dinitrobuta-1,3-diene (4a): 4a was synthesized
according to the standard procedure 1 as yellow oil (0.32 g, 50%). Rf (CCl4) 0.23. IR:
2963, 2926, 2850 (CHaliphatic), 1448 (C C), 1290, 1520 (NO2). UV-Vis: λmax 385 nm (lgε
4.92). 1H NMR: 1.20 (t, 3J = 7.32, 3H, CH3), 1.26 (t, 3J = 7.32, 3H, CH3), 1.28 (t, 3J =
7.32, 3H, CH3), 2.89 [q, 6H, (CH2)]. 13C NMR: 13.38, 13.79, 14.02 (CH3), 26.61, 28.97,
29.75 (CH2), 108.77, 124.04, 127.69, 151.68 (Cbutadien). MS (ESI) m/z 378 [M + Na]+.
Anal. calcd. for C10H15ClN2O4S3 (358.885): C, 33.47; H, 4.21; N, 7.81; S, 26.80; Found:
C, 33.19; H, 4.55; N, 7.49; S, 26.99.
Alternately, 4a was prepared from EtOH (0.04 g, 0.65 mmol) and 2a (0.20 g, 0.65
mmol) in ethanol at 0 ◦C for 1 h (0.20 g, 86%).
1,1,3-Tris(4-bromophenylthio)-4-chloro-2,4-dinitrobuta-1,3-diene (4b): 4b was
synthesized according to the standard procedure 2 as yellow crystals (0.55 g, 42%), mp
◦
152.5–154 C. Rf 0.24 (PE:CHCl3 = 5:1). IR: 3079, 3048 (CHarom), 1470 (C C), 1385,
1
1531 (NO2). UV-Vis: λmax 386 nm (lgε 4.91). H NMR: 6.74–6.77 (m, 4H, CHarom),
6.90–6.93 (m, 4H, CHarom), 7.23–7.32 (m, 4H, CHarom). 13C NMR: 123.62, 125.08,
129.20, 130.15 (Carom), 132.31, 132.60, 132.93, 136.18 (CHarom), 122.13, 128.97, 141.82,
158.22 (Cbutadien). MS (ESI) m/z 742 [M + 2H]+, 643 [M – CClNO2]+. Anal. calcd. for
C22H12Br3ClN2O4S3 (739.702): C, 35.72; H, 1.64; N, 3.79; S, 13.00; Found: C, 35.99; H,
1.81; N, 3.45; S, 13.25.
1,1,3,4-Tetrakis(4-bromophenylthio)-2,4-dinitrobuta-1,3-diene (5a): 5a was syn-
thesized ac◦cording to the standard procedure 2 as yellow crystals (0.48 g, 30%), mp
125.5–127 C. Rf 0.19 (PE:CHCl3 = 5:1). IR: 3073, 3051 (CHarom), 1470 (C C), 1386,
1
1521 (NO2). UV-Vis: λmax 246 nm (lgε 4.86). H NMR: 6.82–6.85 (m, 4H, CHarom),
6.97–7.02 (m, 4H, CHarom), 7.29–7.36 (m, 4H, CHarom). 13C NMR: 120.49, 130.35, 132.08,
132.80, 132.91, 135.52, 137.12, 142.67 (Carom), 123.45, 124.69, 129.65, 130.72 132.40,
132.66, 133.03, 135.83 (CHarom), 120.48, 127.96, 142.67, 157.24 (Cbutadien). Anal. calcd.
for C28H16Br4N2O4S4 (892.314): C, 37.69; H, 1.81; N, 3.14; S, 14.37; Found: C, 37.45; H,
1.58; N, 3.32; S, 14.23.
1,1,3,4-Tetrakis(heptylthio)-2,4-dinitrobuta-1,3-diene (5b): 5b was synthesized
according to the standard procedure 2 as yellow oil (0.47 g, 20%). Rf 0.46 (PE:CHCl3 =
2:1). IR: 2955, 2926, 2855 (CHaliphatic), 1465 (C C), 1292, 1533 (NO2). UV-Vis: λmax 249
nm (lgε 4.51). 1H NMR: 0.82 (t, 3J = 6.84, 12H, CH3), 1.21–1.71 [m, 40H, (CH2)5], 2.81
3
3
(t, 3J = 7.57, 2H, SCH2), 2.86 (t, J = 7.57, 2H, SCH2), 3.00 (t, J = 7.32, 2H, SCH2),
3.06 (t, 3J = 7.32, 2H, SCH2). 13C NMR: 13.00, 13.01, 13.04 (CH3), 21.51, 21.54, 21.58,
27.41, 27.49, 27.61, 27.67, 27.70, 27.72, 27.75, 27.77, 27.78, 27.82, 27.90, 28.00, 28.06,
28.24, 28.39, 28.55, 28.61, 28.79, 28.97, 28.99, 30.54, 30.62, 30.70, 32.38, 33.56, 34.32,
34.76, 35.05, 35.10, 35.21, 35.58, 36.52, 38.25 [(CH2)6], 119.76, 127.15, 142.73, 156.87
(Cbutadien). MS (ESI) m/z 664 [M]+, 580 [M – C6H13]+. Anal. calcd. for C32H60N2O4S4
(665.09): C, 57.79; H, 9.09; N, 4.21; S, 19.28; Found: C, 57.54; H, 9.39; N, 4.51; S, 19.55.
Reactions of Monosulfanyl 2,4-Dinitrobuta-1,3-dienes with Amines;
Standard Procedure 3
A suspension of monosulfanyl-dinitrobuta-1,3-diene 2 in 25 mL CH2Cl2 was added
to a solution of amine in 10 mL CH2Cl2 with two molar equivalent at room temperature.
The mixture was stirred at room temperature for the required reaction time according to
TLC (typically 2–4 h). Then, CHCl3 or CH2Cl2 was added to the reaction mixture. The
organic layer was separated and washed with water (3 × 20 mL) and dried with CaCl2