7208
S. Mondal et al. / Tetrahedron 68 (2012) 7202e7210
a Rheodyne injector equipped with 10
LC syringe pump delivered the solution to the vaporization nozzle
of the electrospray ion source at a flow rate of 3
was used both as a drying gas and for nebulisation with flow rates
of approximately 3 L minꢁ1 and 100 mL minꢁ1, respectively. Pres-
sure in the analyzer region was usually about 3ꢂ10ꢁ5 torr.
m
L loop. A Phoenix 20 micro
(2H, s), 4.74, 4.80 (2ꢂ ABq, J¼16.0 Hz), 6.41 (1H, d, J¼16.4 Hz), 6.58
(1H, d, J¼16.4 Hz), 6.74 (1H, d, J¼16.4 Hz), 7.22 (1H, d, J¼8.8 Hz),
7.28 (1H, d, J¼7.2 Hz), 7.52 (1H, t, J¼8.0 Hz), 7.62e7.65 (2H, m), 7.97
(1H, d, J¼7.2 Hz), 8.02 (1H, d, J¼7.2 Hz), 8.54 (1H, s), 8.56 (1H, d,
J¼16.8 Hz). dC 29.6, 55.9, 57.2, 98.6, 100.8, 117.4, 117.5, 121.1, 126.1,
127.1, 128.8, 129.6, 129.9, 130.3, 130.5, 131.6, 131.7, 132.1, 132.4, 135.5,
137.3, 146.9, 147.1. MS: m/z¼397.13 [MHþ]; HRMS: found 397.1013.
C24H16N2O2SþHþ requires 397.1011.
m
L minꢁ1. Nitrogen
4.2. General procedure for GarratteBraverman and 6p-
electrocyclization reaction and spectral data of the final
compounds
4.2.6. 3,30-Sulfonylbis(methylene)di-2-naphthonitrile (11c) state.
White solid; mp above 270 ꢀC; yield: 19%; Rf¼0.5 (PE/EA¼2:1);
nmax (KBr, cmꢁ1): 2220. dH (DMSO-d6): 5.00 (4H, s), 7.69e7.77
(4H, m), 8.04e8.09 (4H, m), 8.23 (2H, s), 8.67 (2H, s). MS: m/
z¼397.16 [MHþ]; HRMS: found 365.1022. C24H16N2O2SþHþ re-
quires 397.1011.
Sulfone or sulfoxide (10e15 mg) was taken in NMR tube and
dissolved in CDCl3 (600 mL). Catalytic amount of Et3N (10 mol %)
was added and reaction was monitored by recording proton NMR in
different time interval. Reaction mixture was worked up by chlo-
roform/water and the final products were isolated in pure form by
column chromatography (Si-gel, petroleum ether/ethyl acetate
mixture as eluent).
4.2.7. 3-{9-[2-(2-Cyano-vinyl)-phenyl]-2,2-dioxo-2,3-dihydro-1H-
2l
6-naphtho[2,3-c]thiophen-5-yl}-acrylonitrile (10d) state. White
gummy liquid; yield: 99%; Rf¼0.2 (PE/EA¼4:1); nmax (neat, cmꢁ1):
2365, 2219, 1636, 1220, 772. dH 3.98 (1H, d, J¼16.4 Hz), 4.17 (1H, d,
J¼16.4 Hz), 4.66 (2H, s), 5.28 (1H, d, J¼12.0 Hz), 5.83 (1H, d,
J¼11.6 Hz), 6.58 (1H, d, J¼12.0 Hz), 7.29 (1H, d, J¼7.2 Hz), 7.31 (1H,
d, J¼8.4 Hz), 7.53 (1H, t, J¼7.8 Hz), 7.61e7.68 (2H, m), 7.91 (1H, d,
J¼11.6 Hz), 7.97 (1H, s), 8.02 (1H, d, J¼7.2 Hz), 8.35 (1H, d, J¼7.6 Hz).
dC 55.9, 57.1, 98.0, 100.7, 116.3, 116.6, 121.1, 127.2, 128.0, 128.3, 128.6,
129.6, 129.7, 129.9, 130.1, 130.7, 131.0, 131.3, 132.0, 132.5, 136.0, 137.3,
145.7, 146.7. MS: m/z¼419.11 [MNaþ], 397.14 [MHþ]; HRMS: found
397.1018. C24H16N2O2SþHþ requires 397.1011.
4.2.1. 3-{9-[2-(2-Methoxycarbonyl-vinyl)-phenyl]-2,2-dioxo-2,3-
dihydro-1H-2l
6-naphtho[2,3-c]thiophen-5-yl}-acrylic acid methyl
ester (10a) state. Brown solid; mp 110 ꢀC; yield: 59%; Rf¼0.4
(PE/EA¼2:1); nmax (KBr, cmꢁ1): 2924, 2365, 1718, 1636, 1437, 1320,
1173. dH 3.64 (3H, s), 3.89 (3H, s), 4.00, 4.06 (2ꢂ 1H, ABq, J¼16.4 Hz),
4.61, 4.70 (2ꢂ 1H, ABq, J¼16.0 Hz), 6.37 (1H, d, J¼15.6 Hz), 6.55 (1H,
d, J¼15.6 Hz), 7.13 (1H, d, J¼16.0 Hz), 7.21e7.26 (1H, m), 7.38e7.45
(2H, m), 7.54e7.56 (2H, m), 7.78 (1H, d, J¼6.8 Hz), 7.83e7.85 (1H, m),
8.23 (1H, s), 8.50 (1H, d, J¼15.6 Hz). dC 51.7, 51.9, 56.0, 57.3, 120.2,
121.2,121.8,126.1,126.8,127.0,128.3,129.2,129.5,130.6,131.2,132.2,
132.3, 133.4, 136.0, 137.7, 141.1, 141.2, 166.7, 167.0. MS: m/z¼463.13
[MHþ]; HRMS: found 463.1221. C26H22O6SþHþ requires 463.1215.
4.2.8. 3-{9-[2-(2-Methoxycarbonyl-vinyl)-5-nitro-phenyl]-8-nitro-
2,2-dioxo-2,3-dihydro-1H-2l
6-naphtho[2,3-c]thiophen-5-yl}-acrylic
acid methyl ester (10e) state. Brown viscous oil; yield: 64%; Rf¼0.3
(PE/EA¼2:1); nmax (neat, cmꢁ1): 2927, 2364, 1718, 1527, 1322, 1186.
dH 3.77 (4H, d, 13.6 Hz), 3.88 (3H, s), 4.09 (1H, d, J¼16.4 Hz), 4.64,
4.72 (2ꢂ 1H, ABq, J¼16.0 Hz), 6.60e6.64 (2H, m), 7.44 (1H, d,
J¼16.0 Hz), 7.80 (1H, d, J¼8.0 Hz), 7.82e7.87 (2H, m), 7.93 (1H, d,
J¼8.4 Hz), 8.31e8.37 (2H, m), 8.43 (1H, d, J¼16.0 Hz). dC 52.1, 52.3,
56.0, 57.0, 123.2, 124.1, 124.5, 124.6, 124.8, 125.4, 125.5, 128.0,
131.1, 131.7, 132.6, 134.3, 137.3, 139.1, 139.4, 139.7, 147.6, 148.9,
165.9, 166.1. MS: m/z¼575.16 [MNaþ]; HRMS: found 575.0728.
C26H20N2O10SþNaþ requires 575.0736.
4.2.2. Dimethyl 3,30-sulfonylbis(methylene)di-2-naphthoate (11a)
state. White solid; mp 158 ꢀC; yield: 21%; Rf¼0.6 (PE/EA¼2:1); nmax
(KBr, cmꢁ1): 2924, 2361, 1718, 1217, 771. dH 3.80 (6H, s), 5.08 (4H, s),
7.54e7.61 (4H, m), 7.83 (2H, d, J¼7.6 Hz), 7.91 (4H, d, J¼6.4 Hz), 8.55
(2H, d, J¼6.4 Hz). dC 52.3, 56.3, 123.9, 127.5, 127.7, 127.9, 128.7, 132.2,
132.7, 133.3, 134.3, 167.7. MS: m/z¼463.12 [MHþ]; HRMS: found
463.1219. C26H22O6SþHþ requires 463.1215.
4.2.3. 3-{9-[2-(2-Methoxycarbonyl-vinyl)-phenyl]-2,2-dioxo-2,3-
dihydro-1H-2l
6-naphtho[2,3-c]thiophen-5-yl}-acrylic acid ethyl ester
(10b) state. Yellow solid; mp 68 ꢀC; yield: 62%; Rf¼0.4 (PE/EA¼2:1);
nmax (KBr, cmꢁ1): 2926, 2364, 1709, 1636, 1179. dH 1.21 (3H, t,
J¼7.2 Hz), 1.40 (3H, t, J¼7.2 Hz), 4.00, 4.06 (2ꢂ 1H, ABq, J¼16.4 Hz),
4.10 (2H, q, J¼7.2 Hz), 4.34 (2H, q, J¼7.2 Hz), 4.61, 4.70 (2ꢂ 1H, ABq,
J¼16.0 Hz), 6.38 (1H, d, J¼16.0 Hz), 6.55 (1H, d, J¼15.6 Hz), 7.13 (1H,
d, J¼16.0 Hz), 7.22e7.26 (1H, m), 7.38e7.44 (2H, m), 7.53e7.55 (2H,
m), 7.77e7.79 (1H, m), 7.83e7.85 (1H, m), 8.23 (1H, s), 8.48 (1H, d,
J¼15.6 Hz). dC 14.4, 14.6, 56.3, 57.6, 60.8, 61.1, 121.0, 121.6, 122.6,
126.4,127.1,127.2,128.6,129.5,129.7,129.8,130.8,130.9,131.5,132.6,
132.7, 133.8, 136.4, 138.1, 141.2, 141.3, 166.5, 166.9. MS: m/z¼491.24
[MHþ]; HRMS: found 491.1519. C28H26O6SþHþ requires 491.1528.
4.2.9. Dimethyl 3,30-sulfonylbis(methylene)bis(6-nitro-2-
naphthoate) (11e) state. Greenish yellow solid; yield: 23%. Rf¼0.4
(PE/EA¼2:1)dH (DMSO-d6)
d 3.75 (6H, s), 5.17 (4H, s), 8.27e8.34 (4H,
m), 8.40 (2H, s), 8.62 (2H, s) 8.97 (2H, s). MS: m/z¼553.10 [MHþ];
HRMS: found 553.0927. C26H20N2O10SþHþ requires 553.0917.
4.2.10. 3-{9-[2-(2-Methoxycarbonyl-vinyl)-5-nitro-phenyl]-8-nitro-
2,2-dioxo-2,3-dihydro-1H-2l
6-naphtho[2,3-c]thiophen-5-yl}-acrylic
acid ethyl ester (10f) state. Yellow solid; mp 130 ꢀC; yield: 52%;
Rf¼0.4 (PE/EA¼2:1); nmax (KBr, cmꢁ1): 2928, 2365, 1718, 1528, 1321,
1186. dH 1.29 (3H, t, J¼7.2 Hz), 1.41 (3H, t, J¼7.2 Hz), 3.76 (1H, d,
J¼16.4 Hz), 4.10 (1H, d, J¼16.4 Hz), 4.21 (2H, q, J¼7.2 Hz), 4.37 (2H,
q, J¼7.2 Hz), 4.64, 4.72 (2ꢂ 1H, ABq, J¼16.0 Hz), 6.61 (1H, d,
J¼15.6 Hz), 6.63 (1H, d, J¼16.0 Hz), 7.43 (1H, d, J¼16.0 Hz), 7.81 (1H,
d, J¼8.0 Hz), 7.83 (1H, d, J¼8.0 Hz), 7.87 (1H, d, J¼2.4 Hz), 7.49 (1H,
d, J¼8.8 Hz), 8.33e8.37 (2H, m), 8.42 (1H, d, J¼16.0 Hz). dC 14.2,14.3,
56.1, 57.0, 61.2, 61.4, 123.0, 123.3, 124.2, 124.6, 124.9, 125.1, 125.4,
126.0,128.0,131.2,131.7,132.6,134.4,137.4,137.5,138.9,139.2,139.9,
147.6, 149.0, 165.6, 165.8. MS: m/z¼581.19 [MHþ]; HRMS: found
581.1233. C28H24N2O10SþHþ requires 581.1230.
4.2.4. Diethyl 3,30-sulfonylbis(methylene)di-2-naphthoate (11b)
state. Gummy oil; yield: 23%; Rf¼0.7 (PE/EA¼2:1); nmax (neat, cmꢁ1):
2294, 2363,1718,1560,1219, 772. dH 1.38 (6H, d, J¼7.2 Hz), 4.35 (4H, q,
J¼7.2 Hz), 5.09 (4H, s), 7.56e7.60 (4H, m), 7.82 (2H, d, J¼7.6 Hz), 7.92
(4H, d, J¼8.4 Hz), 8.55 (2H, s). dC 14.2, 56.4, 61.5, 124.1, 127.5, 128.3,
128.6, 128.8, 132.3, 132.6, 133.3, 134.3, 167.4. MS: m/z¼491.08 [MHþ];
HRMS: found 491.1523. C28H26O6SþHþ requires 491.1528.
4.2.5. 3-{9-[2-(2-Cyano-vinyl)-phenyl]-2,2-dioxo-2,3-dihydro-1H-
2
l
6-naphtho[2,3-c]thiophen-5-yl}-acrylonitrile (10c) state. White
4.2.11. Diethyl 3,30-sulfonylbis(methylene)bis(6-nitro-2-naphthoate)
(11f) state. Yellow solid; mp 114 ꢀC; yield: 41%; Rf¼0.5
(PE/EA¼2:1); nmax (KBr, cmꢁ1): 2923, 2365, 1718,1560, 1220. dH 1.44
solid; mp above 270 ꢀC; yield: 65%; Rf¼0.4 (PE/EA¼2:1); nmax
(KBr, cmꢁ1): 2925, 2345, 2218, 1654, 1560, 1315. dH (DMSO-d6) 4.13