Studies on Bis-o-quinodimethanes
J. Chin. Chem. Soc., Vol. 49, No. 1, 2002 81
1,2,4,5-Tetra(bromomethyl)ben zene 16
4H), 3.02-2.96 (m, 4H); c 178.27 (Cq), 134.22 (Cq), 131.40
(Cq), 128.89 (CH), 128.47 (CH), 127.40 (CH), 126.22 (CH),
40.17 (CH), 29.42 (CH2); MS (EI) m/z 476 (M+, 71), 328
(100), 179 (51), 165 (51).
A white solid;11 mp 150-152 C; H 7.38 (s, 2H), 4.60 (s,
8H); C 137.58 (Cq), 133.58 (CH), 28.66 (CH2).
4,6,7,9-Tetrahydro-1H,3H-3 4,7 4-[1,2]oxathiino[5 ,4 :4,5]-
benzo[d][1,2]oxathiine-3,7-diones 17 and 18
7-Phenyl-1,2,3,5,5a,6,7,8,8a,9-decahydro-2 6-thieno-
[3 ,4 :4,5]benzo[f]isoindole-2,2,6,8-tetraone 22
Asolutionof16 (1.0 g, 2.22 mmol), Rongalite (1.71 g,
11.10 mmol) and TBAB (0.36 g, 1.12 mmol) in DMF (10 mL)
was stirred at rt for 6 h. The mix ture was di luted with H2O (10
mL) and ex tracted three times with CH2Cl2. The or ganic layer
was dried over MgSO4. Evap o ra tion of the sol vent and the
residuewaspurifiedbycolumnchromatography(EtOAc/
hex ane, 1:3) to give a mix ture of 17 and 18 (0.32 g, 56%). 17
and 18: H 7.11-7.17 (m, 4H), 4.97, 5.30 (A B q, J = 13.8 Hz,
8H), 4.40, 4.30 (ABq, J= 15.0 Hz, 4H), 3.62, 3.56 (A B q, J =
14% yield, a white solid; mp 240-241 C; H 6.79-7.33
(m, 7H), 4.25 (s, 4H), 2.89-3.44 (m, 6H); c 178.03 (Cq),
136.12 (Cq), 131.42 (Cq), 130.39 (Cq), 129.15 (CH), 128.78
(CH), 126.20 (CH), 125.56 (CH), 56.66 (CH2), 39.86 (CH),
29.80 (CH2); MS (EI) m/z 367 (M+, 10), 335 (100), 179 (21).
1,2,3,4,5,6,7,8-octahydroanthracene-2,2,3,3,6,6,7,7-otacar-
bonitrile 23
15.0 Hz, 4H);
133.32 (Cq), 132.83 (Cq), 131.54 (CH),
63% yield, a brown solid; mp 270 C (lit.9a > 200 C);
1HNMR(300MHz,acetone-d6) H 7.48 (s, 2H), 4.25 (s, 8H);
13CNMR(75MHz,acetone-d6) C 130.76 (CH), 127.58 (Cq),
111.78 (Cq), 39.71 (Cq), 34.66 (CH2); MS (EI) m/z 386 (M+,
8), 258 (100). HRMS calcd for C22H10N8 386.1031, found
386.1004.
C
131.02 (CH), 127.14 (CH), 126.74 (Cq), 126.12 (Cq), 125.54
(Cq), 123.06 (CH), 122.80 (CH), 62.40 (CH2), 62.32 (CH2),
56.31 (CH2), 55.64 (CH2); HRMS (EI) calcd for C10H10O4S2
258.0021, found 258.0019.
General Procedure for the Trapping Experiments of
Benzodisultines 17 and 18 with Dienophiles such as
Fumaronitrile, N-Phenylmaleimide, Tetracyanoethylene,
Dimethyl Acetylenedicarboxylate, and Diethyl Fumarate
A so lu tion mix ture of benzodisultines17 and 18 (40
mg, 0.16 mmol), with re spec tive dienophiles (0.93 mmol), in
xylenes (3 mL) was heated at 200 C in a sealed tube un der N2
for 10 min. The sol vent was evap o rated un der vac uum, and
theresiduewassubjectedtosilicagelchromatographyusing
hex ane/ethyl ac e tate (from 2:1 to 8:1) as the eluent. Re spec-
tive yields for the trap ping ex per i ments with var i ous dieno-
philes are sum ma rized in Scheme IV.
Tetramethyl 1,4,5,8-tetrahydro-2,3,6,7-anthracenetetra-
car boxylate 24
22% yield, a white solid; mp 206-208 C; 1H NMR (300
MHz, CDCl3) H 6.97 (s, 2H), 3.83 (s, 12H), 3.68 (s, 8H);13C
NMR (75 MHz, CDCl3) c 168.06 (Cq), 133.29 (Cq), 130.13
(Cq), 127.20 (CH), 52.38 (CH3), 31.04 (CH2); MS (EI) m/z
414 (M+, 7), 382 (100), 323 (23), 263 (17), 178 (41).
Dimethyl 2,2-dioxo-2,3,5,8-tetrahydro-1H-2 6-naphtho-
[2,3-c]t hiophene-6,7-dicarboxylate 25
49% yield, a white solid, mp 210-211 C;
7.13 (s,
H
2H), 4.33 (s, 4H), 3.84 (s, 6H), 3.72 (s, 4H); c 167.65 (Cq),
132.85 (Cq), 132.63 (Cq), 129.79 (Cq), 125.44 (CH), 56.55
(CH2), 52.45 (CH3), 31.24 (CH2); MS (EI) m/z 336 (M+, 8),
304 (100), 277 (42), 239 (82), 212 (52), 181 (45), 154 (65).
HRMS calcd for C16H16O6S 336.0668, found 336.0613.
6
2,2-Dioxo-2,3,5,6,7,8-hexahydro-1H-2 -naphtho[2,3-c]-
thiophene-6,7-dicarbonitrile 20
41% yield; a white solid, mp 228-229 C;
7.14 (s,
H
2H), 4.34 (s, 4H), 3.46-3.33 (m, 4H), 3.21-3.15 (m, 2H); c
131.11 (Cq), 130.82 (Cq), 126.71 (CH), 118.00 (Cq), 56.46
(CH2), 29.92 (CH2), 28.02 (CH); MS (EI) m/z 272 (M+, 2),
208 (100), 130 (15), 117 (22). HRMS calcd for C 14H12N2O2S:
272.0620, found 272.0622.
Tetraethyl 1,2,3,4,5,6,7,8-octahydro-2,3,6,7-anthracene-
tetracarboxylate 269b
40% yield, a white solid; mp 142-144 C; 1H NMR (300
MHz, CDCl3)
6.83 (s, 2H), 4.18 (q, J = 7.2 Hz, 8H),
H
2,8-Diphenyl-1,2,3,3a,4,6,6a,7,8,9,9a,10,12,12a-Tetradeca-
hydropyrrolo[3 ,4 :6,7]naphtho[2,3-f]isoindole-1,3,7,9-
tetraone 21
3.11-2.89 (m, 12H), 1.28 (t, J = 7.1 Hz, 12H); 13C NMR (75
MHz, CDCl3) c 174.35 (Cq), 131.95 (Cq), 128.34 (CH),
60.73 (CH2), 42.16 (CH3), 31.33 (CH2), 14.11 (CH3); MS (EI)
m/z 474 (M+, 12), 400 (30), 355 (15), 326 (37), 281 (25), 253
(29), 179 (100). HRMS calcd for C26H34O8 474.2254, found
16% yield, a white solid; mp > 270 C; H 7.16-7.09 (m,
8H), 6.83-6.80 (m, 4H), 3.41-3.39 (m, 4H), 3.20-3.14 (m,