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L. Bianchi et al. / Tetrahedron 65 (2009) 336–343
td, J 13.4 and 4.3 Hz), 4.12 (1H, t, J 13.8 Hz), 4.42 (1H, dd, J 13.8 and
4.7 Hz), 7.15 (4H, AA0BB0 system); 13C NMR (CD3COCD3)
21.03,
38.74, 50.62, 53.43, 55.73, 129.75, 129.77, 134.11, 137.78, 202.84; MS
(ESI): m/z 260.9 (MþNa)þ, 236.9 (Mꢀ1); HRMS calcd for C12H14O3S:
238.0664; found 238.0664.
4.6.3. N-(2,4-Dinitrophenyl)-N0-[1,1-dioxo-3-(3-methylphenyl)-
d
tetrahydro-1l
6-thiopyran-4-ylidene]hydrazine (13c)
Yield 0.092 g, 28%; orange solid, mp 246–247 ꢁC (ethanol/di-
oxane); nmax (Nujol) 3327, 1616, 1594, 1533, 1500, 1334, 1294, 1192,
1120, 1088 cmꢀ1; 1H NMR (CD3SOCD3)
d 2.35 (3H, s), 2.86–2.97 (1H,
m), 3.25 (1H, dt, J 11.1 and 4.8 Hz), 3.45–3.56 (3H, m), 4.02 (1H, t, J
13.2 Hz), 4.40 (1H, dd, J 12.3 and 4.2 Hz), 7.14–7.20 (4H, m), 7.29 (1H,
t, J 7.5 Hz), 8.24 (1H, dd, J 9.3 and 2.4 Hz), 8.81 (1H, d, J 3.0 Hz), 10.93
4.5.5. 1,1-Dioxo-3-(4-methoxyphenyl)tetrahydro-1l
6-thiopyran-4-
one (12e)
Yield 0.083 g, 82%; pale brown solid (methylene chloride/light
(1H, s); 1H NMR (CD3COCD3)
d 2.39 (3H, s), 3.07–3.15 (1H, m), 3.43–
petroleum); 1H NMR (CD3COCD3)
d
2.79 (1H, dt, J 15.3 and 4.4 Hz),
3.67 (4H, m), 4.00 (1H, t, J 12.6 Hz), 4.52 (1H, dd, J 12.3 and 3.9 Hz),
7.19–7.39 (5H, m), 8.24 (1H, br d, J 9.9 Hz), 8.96 (1H, br s), 11.14 (1H,
3.23 (1H, ddd, J 15.3, 12.9 and 5.1 Hz), 3.35–3.50 (2H, m), 3.77–3.87
(4H, m), 4.10 (1H, t, J 13.5 Hz), 4.41 (1H, dd, J 13.8 and 4.8 Hz), 6.90
(2H, half AA0BB0, J 8.7 Hz), 7.17 (2H, half AA0BB0, J 9.0 Hz); 13C NMR
br s); 13C NMR (CD3SOCD3)
d 20.95, 24.19, 47.38, 48.22, 54.76,
115.49, 122.81, 125.90, 127.71, 127.87, 129.44, 129.63, 129.81, 137.01,
137.21, 137.43, 144.75, 155.85; MS (ESI): m/z 441 (MþNa)þ, 417
(Mꢀ1); HRMS calcd for C18H18N4O6S: 418.0947; found 418.0941.
Anal. Calcd for C18H18N4O6S (418.42): C, 51.67; H, 4.34; N, 13.39%.
Found: C, 51.58; H, 4.34; N, 13.33%.
(CD3COCD3)
d 38.69, 50.62, 53.03, 55.47, 55.89, 114.51, 129.05,
130.95, 160.03, 203.01; HRMS calcd for C12H14O4S: 254.0613; found
254.0612.
4.5.6. 3-(4-Chlorophenyl)-1,1-dioxotetrahydro-1l
6-thiopyran-4-
one (12f)
4.6.4. N-(2,4-Dinitrophenyl)-N0-[1,1-dioxo-3-(4-methylphenyl)-
Yield 0.084 g, 81%; pale brown solid (methylene chloride/light
tetrahydro-1l
6-thiopyran-4-ylidene]hydrazine (13d)
petroleum); 1H NMR (CD3COCD3)
d
2.81 (1H, dt, J 15.6 and 4.2 Hz),
Yield 0.099 g, 30%; orange solid, mp 248–252 ꢁC (ethanol/di-
3.26 (1H, ddd, J 15.6, 13.5 and 5.1 Hz), 3.42–3.52 (2H, m), 3.85 (1H,
td, J 13.5 and 4.5 Hz), 4.16 (1H, t, J 13.5 Hz), 4.53 (1H, dd, J 13.8 and
4.8 Hz), 7.30 (2H, half AA0BB0, J 8.7 Hz), 7.39 (2H, half AA0BB0,
oxane); nmax (Nujol) 3328, 1739, 1614, 1596, 1535, 1500, 1360, 1335,
1314, 1294, 1244, 1174, 1138, 1122, 1090, 1063, 1029 cmꢀ1 1H NMR
;
(300, CD3SOCD3)
d 2.34 (3H, s), 2.91 (1H, app q), 3.24 (1H, app dt),
J 8.7 Hz); 13C NMR (CD3COCD3)
d
38.69, 50.55, 53.07, 55.30, 129.11,
3.40–3.56 (3H, m), 4.01 (1H, t, J 12.9 Hz), 4.40 (1H, dd, J 12.2 and
3.8 Hz), 7.15–7.28 [5H in all, AA0BB0(J 7.8 Hz) and d (J 9.6 Hz)], 8.27
(1H, dd, J 9.6 and 2.3 Hz), 8.82 (1H, d, J 2.3 Hz), 10.94 (1H, s); 1H
131.71, 133.64, 135.95, 202.46; HRMS calcd for C11H11ClO3S:
258.0117; found 258.0115.
NMR (CD3COCD3)
d 2.39 (3H, s), 3.04–3.17 (1H, m), 3.40–3.69 (4H,
4.6. Derivatization of ketones 12 as 2,4-
dinitrophenylhydrazones 13
m), 3.98 (1H, t, J 13.1 Hz), 4.53 (1H, dd, J 12.6 and 4.2 Hz), 7.26 (2H,
half AA0BB0, J 8.0 Hz), 7.34 (2H, half AA0BB0, J 8.0 Hz), 7.40 (1H, d, J
9.6 Hz), 8.23 (1H, dd, J 9.6 and 2.7 Hz), 8.95 (1H, d, J 2.7 Hz), 11.20
To a solution of the appropriate crude 12 (0.8 mmol) in ethanol
(2.5 mL), 2,4-dinitrophenylhydrazine (0.88 mmol) in ethanol
(5 mL) and HCl 37% (0.75 mL) were added and the reaction mixture
kept at 100 ꢁC under magnetic stirring for 10 min. The hydrazones
13a–f, which separated as orange powders, were filtered and
crystallized.
(1H, br s); 13C NMR (CD3SOCD3)
d 20.65, 24.15, 47.03, 48.19, 54.87,
115.56, 122.78, 128.54, 128.59, 129.61, 129.86, 134.49, 136.13, 137.18,
144.73, 156.04; MS (ESI): m/z 441 (MþNa)þ, 417 (Mꢀ1); HRMS
calcd for C18H18N4O6S: 418.0947; found 418.0948. Anal. Calcd for
C18H18N4O6S (418.42): C, 51.67; H, 4.34; N, 13.39%. Found: C, 51.54;
H, 4.35; N, 13.34%.
4.6.1. N-(2,4-Dinitrophenyl)-N0-(1,1-dioxo-3-phenyltetrahydro-
4.6.5. N-(2,4-Dinitrophenyl)-N0-[1,1-dioxo-3-(4-methoxyphenyl)-
1
l
6-thiopyran-4-ylidene)hydrazine (13a)
tetrahydro-1
Yield 0.081 g, 23%; yellow solid, mp 241–242 ꢁC (ethanol/di-
oxane); nmax (Nujol) 3330, 1614, 1336, 1116, 1023 cmꢀ1 1H NMR
(CD3SOCD3) 2.90 (1H, app q), 3.20–3.30 (1H, m), 3.45 (1H, d, J
l
6-thiopyran-4-ylidene]hydrazine (13e)
Yield 0.048 g, 15%; orange solid, mp 263–265 ꢁC (ethanol/di-
oxane); nmax (Nujol) 3326,1615,1595,1500,1335,1120 cmꢀ1; 1H NMR
;
(CD3SOCD3)
d
2.87–2.98 (1H, m), 3.30 (1H, app dt), 3.49–3.57 (3H, m),
d
4.05 (1H, t, J 12.9 Hz), 4.46 (1H, dd, J 12.6 and 3.9 Hz), 7.12 (1H, d,
J 9.4 Hz), 7.32–7.44 (5H, m), 8.22 (1H, dd, J 9.4 and 2.5 Hz), 8.82 (1H,
13.5 Hz), 3.50–3.58 (2H, m), 3.79 (3H, s), 3.99 (1H, t, J 12.9 Hz),
4.40 (1H, dd, J 12.9 and 4.2 Hz), 6.96 (2H, half AA0BB0, J 8.7 Hz),
7.21 (1H, d, J 9.6 Hz), 7.30 (2H, half AA0BB0, J 8.4 Hz), 8.29 (1H,
dd, J 9.3 and 2.4 Hz), 8.82 (1H, d, J 2.7 Hz), 10.95 (1H, s); 13C
dd, J 2.5 Hz),10.94 (1H, s); 13C NMR (CD3SOCD3)
d 24.22, 47.39, 48.24,
54.66, 115.47, 122.82, 127.11, 127.98, 128.81, 129.65, 129.87, 137.23,
137.56,144.72,155.91;MS(ESI):m/z427 (MþNa)þ, 403(Mꢀ1);HRMS
calcd for C17H16N4O6S: 404.0791; found 404.0792.
NMR (CD3SOCD3)
d 24.16, 46.68, 48.23, 55.00, 55.10, 113.40,
115.58, 122.85, 129.42, 129.62, 129.87, 129.97, 137.19, 144.76,
156.22, 158.24; MS (ESI): m/z 435 (MþH)þ, 457 (MþNa)þ. Anal.
Calcd for C18H18N4O7S (434.47): C, 49.76; H, 4.18; N, 12.90%.
Found: C, 49.68; H, 4.16; N, 12.91%.
4.6.2. N-(2,4-Dinitrophenyl)-N0-[1,1-dioxo-3-(2-methylphenyl)-
tetrahydro-1l
6-thiopyran-4-ylidene]hydrazine (13b)
Yield 0.073 g, 22%; orange solid, mp 196–197 ꢁC (ethanol/di-
oxane); nmax (Nujol) 3331, 1617, 1595, 1559, 1499, 1335, 1310, 1294,
4.6.6. N-[3-(4-Chlorophenyl)-1,1-dioxotetrahydro-1l
6-thiopyran-
1282, 1192, 1123, 1083 cmꢀ1
;
1H NMR (CD3SOCD3)
d
2.27 (3H, s),
4-ylidene]-N0-(2,4-dinitrophenyl)hydrazine (13f)
2.87–3.00 (1H, m), 3.3 ca. (1H, app dt), 3.45–3.65 (3H, m), 4.08 (1H,
t, J 13.3 Hz), 4.51 (1H, dd, J 12.6 and 2.7 Hz), 6.98 (1H, d, J 9.6 Hz),
7.20–7.35 (4H, m), 8.18 (1H, dd, J 9.6 and 2.1 Hz), 8.80 (1H, d,
Yield 0.123 g, 35%; yellow solid, mp 249–250 ꢁC (ethanol/di-
oxane); nmax (Nujol) 3327, 1616, 1594, 1499, 1337, 1312, 1289, 1121,
1090 cmꢀ1; 1H NMR (CD3SOCD3)
d 2.91 (1H, app q), 3.24–3.29 (1H,
J 2.1 Hz),10.93 (1H, s); 1H NMR (CD3COCD3)
d
2.35 (3H, s), 3.06–3.20
m), 3.50–3.55 (3H, m), 4.03 (1H, t, J 12.9 Hz), 4.49 (1H, dd, J 12.3 and
3.9 Hz), 7.15 (1H, d, J 9.6 Hz), 7.42 (2H, half AA0BB0, J 8.7 Hz), 7.47
(2H, half AA0BB0, J 8.7 Hz), 8.29 (1H, dd, J 9.6 and 2.4 Hz), 8.82 (1H, d,
(1H, m), 3.40–3.74 (4H, m), 4.05 (1H, t, J 13.4 Hz), 4.72 (1H, dd, J 13.4
and 3.8 Hz), 7.15–7.41 (5H, m), 8.16 (1H, dd, J 9.6 and 2.4 Hz), 8.93
(1H, d, J 2.4 Hz), 11.13 (1H, s); 13C NMR (CD3SOCD3)
d
19.20, 24.43,
J 2.7 Hz), 10.94 (1H, s); 13C NMR (CD3SOCD3)
d 24.26, 46.74, 48.26,
43.65, 48.25, 54.19, 115.24, 122.84, 125.65, 126.97, 127.94, 129.59,
129.78, 129.88, 135.89, 135.96, 137.17, 144.77, 155.55; MS (ESI): m/z
441 (MþNa)þ, 417 (Mꢀ1). Anal. Calcd for C18H18N4O6S (418.42): C,
51.67; H, 4.34; N, 13.39%. Found: C, 51.54; H, 4.30; N, 13.34%.
54.52, 115.49, 122.86, 127.99, 129.75, 130.01, 130.78, 131.73, 136.62,
137.26, 144.70, 155.86; MS (ESI): m/z 439 (MþH)þ, 461 (MþNa)þ.
Anal. Calcd for C17H15ClN4O6S (438.88): C, 46.52; H, 3.45; N, 12.77%.
Found: C, 46.50; H, 3.40; N, 12.70%.