2558 J . Org. Chem., Vol. 61, No. 7, 1996
Notes
phase washed once with methylene chloride (50 mL). The
combined organics were dried over Na2SO4 and the solvents
removed in vacuo. 3 was vacuum dried at 45 °C for 2 h. Yield:
11.93 g, 95%. An analytical sample was prepared by recrystal-
lization from petroleum ether. Mp: 103-104 °C. 1H NMR
(CDCl3): δ 7.42 (5H, s), 6.65 (1H, s), 3.54 (2H, d, J ) 7 Hz), 1.95
(2H, d, J ) 9 Hz), 1.69 (1H, d, J ) 9 Hz), 1.42 (1H, d, J ) 9 Hz),
1.22 (2H, d, J ) 7 Hz). 13C NMR (CDCl3): δ 184.64, 183.74 ,
151.87, 151.50, 133.23, 132.58, 129.68, 129.31, 128.39, 47.78,
41.02, 40.67, 25.16, 25.12. IR (KBr) 3450, 1640, 1580, 1340,
were dissolved in 30 mL of tetrahydrofuran and stirred for 5 h
at ambient temperature until the quinone was completely
consumed (TLC 3:1 chloroform:hexanes). The solvents were
removed in vacuo. The crude reaction mixture was chromato-
graphed on silica gel using 30% hexanes in methylene chloride
as eluent. Hydroquinone 6 was eluted as the first product (15%
yield). Enedione 7 was the second product eluted (12% yield).
6 Mp: 173-175 °C. 1H NMR(CDCl3): δ 10.00 (1H, s), 7.28.
(1H, d, J ) 8 Hz), 7.19 (2H, d, J ) 5 Hz), 7.09 (2H, d, J ) 8 Hz),
6.99 (2H, d, J ) 8 Hz), 6.90 (1H, dd, J ) 3,5), 6.79 (1H, s), 6.77
(2H, t, J ) 3 Hz), 4.33 (1H, s), 4.17 (2H, d, J ) 10 Hz), 2.35 (3H,
s), 2.30 (2H, s). 13C NMR (CDCl3): δ 146.54, 145.85, 143.90,
143.38, 142.08, 141.55, 141.48, 139.23, 131.82, 131.70, 131.62,
129.13, 128.66, 128.53, 126.90, 125.45, 118.34, 70.44, 47.86,
47.34, 21.60. IR (KBr) 3425, 3280, 2960, 1425, 1335, 1260, 1200,
1120, 1070 cm-1. MS (EI+): 405 (M). An analytical sample was
prepared by recrystallization from hexanes. Anal. Calcd for
C24H20O4S: C, 71.27; H, 4.98; S, 7.93. Found: C, 71.02; H, 5.04;
S, 8.21.
7. Mp: 144-145 °C. 1H NMR(DMSO-d6): δ 7.72 (1H, d, J
) 7 Hz), 7.4 (8H, complex multiplets), 6.88 (1H, s), 6.31 (1H, t,
J ) 3 Hz), 6.01 (1H, t, J ) 3 Hz), 4.12 (1H, d, J ) 4 Hz), 3.62
(1H, s), 3.37 (1H, s), 2.45 (3H, s), 2.21 (1H, d, J ) 9 Hz), 1.45
(1H, d, J ) 9 Hz). 13C NMR (DMSO-d6): δ 195.4, 191.3, 151.0,
146.0, 139.4, 137.4, 136.2, 132.6, 132.2, 130.4, 130.1, 129.9, 129.0,
128.4, 79.8, 51.9, 51.5, 47.2, 44.9, 21.2. IR (KBr) 3050, 3020,
1670, 1590, 1310, 1280, 1220, 1130 cm-1. MS (EI+): 405 (M).
An analytical sample was prepared by recrystallization from
2-propanol. Anal. Calcd for C24H20O4S: C, 71.27; H, 4.98; S,
7.93. Found: C, 71.31; H, 4.97; S, 8.05.
1260, 1220 cm-1
.
MS (EI+): 250. Anal. Calcd for C17H14O2:
C, 81.58; H, 5.64. Found: C, 81.38; H, 5.38.
1,2,3,4-Tetr ah ydr o-6-ph en yl-7-(tolu en esu lfon yl)-1,4-m eth -
a n on a p h th a len e-5,8-d iol (4). p-Toluenesulfinic acid (1.56 g,
0.01 mol) and 1,2,3,4-tetrahydro-6-phenyl-1,4-methanonaphtha-
lene-5,8-dione, 3, (1.25 g, 5.0 mmol) were dissolved in tetrahy-
drofuran (20 mL) and stirred for 5 h at ambient temperature
until 3 was completely consumed (TLC 3:1 chloroform:hexanes).
The reaction was diluted with methylene chloride (30 mL), and
silica gel (10 g) and MgSO4 (10 g) were added. This mixture
was filtered, and the solvents were removed in vacuo. Recrys-
tallization from 2-propanol (15 mL) afforded 4. Yield: 1.30 g,
64%. Mp: 157-158 °C. 1H NMR (CDCl3): δ 10.05 (1H, s), 7.2
(8H, complex multiplets), 6.67 (1H, d, J ) 8 Hz), 3.76 (1H, s),
3.58 (1H, s), 4.16 (1H, s), 2.37 (3H, s), 1.96 (2H, m), 1.78 (1H, d,
J
) 6 Hz), 1.53 (1H, dd, J ) 6, 2 Hz), 1.27 (2H, complex
multiplets). 13C NMR (CDCl3): δ 145.48, 143.83, 142.32, 140.55,
139.31, 137.64, 132.34, 131.80, 131.26, 129.12, 128.58, 128.54,
128.44, 126.88, 124.79, 118.20, 48.94, 40.93, 40.40, 25.91, 25.85,
21.60. IR (KBr) 3500, 3250, 2950, 2875, 1420, 1320, 1290, 1260,
1210, 1150, 1110, 1070 cm-1. MS (EI+) ) 406. Anal. Calcd for
C24H22O4S: C, 70.91; H, 5.46; S, 7.89. Found: C, 70.51; H, 5.60;
S, 7.94.
Alter n a te Syn th esis of 7. 9 (1.00 g, 3 mmol) was dissolved
in benzene (10 mL). Freshly distilled cyclopentadiene (0.22 g,
3.3 mmol) was added and an immediate color change to pale
yellow was observed. The reaction solution was stirred for 1 h,
and the solvents were removed in vacuo. 7 was recrystallized
from 2-propanol (25 mL) and dried for 16 h at 60 °C and 15
mmHg. Yield ) 1.04 g, 87%.
1,4-Dih yd r o-6-p h en yl-1,4-m et h a n on a p h t h a len e-5,8-d i-
on e (5). 5 was prepared by the same method described for 3
from 1,4-dihydro-6-phenyl-1,4-methanonaphthalene-5,8-diol.
Yield: 23.3 g, 94%. An analytical sample was prepared by
recrystallization from diethyl ether. Mp: 117-118 °C. 1H NMR
(CDCl3): δ 7.42 (5H, s), 6.89 (2H, s), 6.64 (1H, s), 4.15 (2H, s),
2.34 (2H, s). 13C NMR (CDCl3): δ 184.15, 183.33, 161.01, 160.57,
145.50, 142.71, 142.51, 133.19, 132.26, 129.68, 129.35, 128.39,
73.79, 48.72, 48.42. IR (KBr) 3450, 1650, 1560, 1330, 1280, 1260
cm-1. MS (EI+): 248. Anal. Calcd for C17H12O2: C, 82.24; H,
4.87. Found: C, 82.13; H, 4.68.
P en t a cyclo[5.4.0.02,6.03,10.05,9]-10-p h en yl-1-(t olu en esu l-
fon yl)u n d eca n e-8,11-d ion e (8). A solution of 7 (0.5 g) in
benzene (6 mL) was irradiated with a Hg lamp for 2 h at ambient
temperature. The product crystallized out of solution. Quan-
titative yields can be obtained by removing the solvent in vacuo.
1H NMR spectroscopy indicated clean cyclization to 8. Mp: 196-
197 °C. 1H NMR (CDCl3): δ 3.68 (1H, d, J ) 9 Hz), 3.58 (1H,
m), 3.36 (1H, m), 3.29 (1H, m), 3.18 (1H, m), 2.94 (1H, m), 2.88
(1H, d, J ) 12 Hz), 2.43 (3H, s), 2.06 (1H, d, J ) 12 Hz). 13C
NMR (CDCl3): δ 207.57, 201.43, 145.64, 134.38, 133.51, 130.66,
129.56, 128.67, 128.51, 127.86, 126.87, 80.40, 57.39, 55.68, 51.74,
47.95, 44.65, 43.21, 40.70, 37.05, 21.76. MS (EI+): 404. IR (KBr)
2-P h en yl-6-(tolu en esu lfon yl)ben zen e-1,4-d iol. Sodium p-
toluenesulfinate heptahydrate (6.09 g, 0.02 mol) and phenyl-
benzoquinone (3.68, 0.02 moles) were reacted in acetic acid (40
mL) for 30 min at 80 °C. Water (80 mL) was added, and the
reaction mixture chilled to 5 °C and then filtered. The collected
white precipitate was recrystallized from toluene (100 mL) to
give 2-phenyl-6-(toluenesulfonyl)benzene-1,4-diol. Yield: 3.58
g, 52%. An analytical sample was prepared by a second
recrystallization from toluene. Mp: 180-181 °C. 1H NMR
(CDCl3): δ 8.79 (1H, s), 7.78 (2H, d, J ) 8 Hz), 7.42 (1H, d, J )
1 Hz), 7.36 (1H, s), 7.26 (2H, d, J ) 8 Hz), 7.15 (1H, d, J ) 3
Hz), 6.98 (1H, d, J ) 3 Hz), 5, (1H, s), 2, (3H, s). 13C NMR
(DMSO-d6): δ 150.48, 144.30, 143.88, 138.38, 136.72, 133.77,
129.74, 129.53, 129.11, 128.29, 127.73, 127.50, 123.36, 113.27,
21.03. MS (EI+): 340. IR (KBr) 3420, 3360, 1600, 1460, 1430,
3440, 2980, 1750, 1600, 1320, 1300, 1150, 1080 cm-1
. Anal.
Calcd for C24H20O4S: C, 71.27; H, 4.98; S, 7.93. Found: C, 71.07;
H, 4.98; S, 8.09.
X-r a y An a lysis. The crystal structure of 7 was determined
using Mo KR radiation and a Nicolet autodiffractometer at 293
( 1 K. 7 crystallized as triclinic pale yellow parallelepipeds with
unit cell dimensions of a ) 6.883(1) Å, b ) 8.132(2) Å, c )
17.651(4) Å, R ) 87.01(3)°, â ) 84.34(3)°, γ ) 81.74(3)° and space
group P-1. Z ) 2, density (calcd) ) 1.382 mg/cm3, 4455
independent reflections (Rint ) 1.79%), final R ) 4.61%. Struc-
ture solution and refinement was carried out using the Siemens
SHELXTL PLUS (PC Version). A molecular thermal ellipsoid
plot is included in the supporting information; cell dimensions,
atom coordinates, and other crystal data have been deposited
with the Cambridge Crystallographic Data Centre.
1250, 1220, 1130, 1080 cm-1
. Anal. Calcd for C19H16O4S: C,
67.04; H, 4.74; S, 9.42. Found: C, 66.69; H, 4.75; S, 9.67.
2-P h en yl-6-(t olu en esu lfon yl)b en zen e-1,4-d ion e
(9).
2-Phenyl-6-(toluenesulfonyl)benzene-1,4-diol (3.40 g, 0.01 mol)
was treated with o-chloranil (2.46 g, 0.01 mol) in acetone (30
mL). After 4 h, hexanes (30 mL) were added, and the reaction
mixture was chilled to 5 °C. 9 crystallized out of solution and
was isolated by filtration as yellow needles. Yield: 1.92 g, 57%.
Mp: 160-161 °C. 1H NMR (CDCl3): δ 7.98 (2H, d, J ) 8 Hz),
7.66 (1H, d, J ) 3 Hz), 7.40 (7H, complex multiplets), 6.90 (1H,
d, J ) 3 Hz), 2.44 (3H, s). 13C NMR (CDCl3): δ 185.69, 180.75,
146.72, 146.14, 145.97, 136.94, 135.34, 132.88, 131.60, 130.73,
129.94, 129.69, 129.42, 128.66, 21.77. MS (EI+): 338. IR (KBr)
Ack n ow led gm en t. We would like to thank Dr.
Gerald Dudek for providing the mass spectral data for
the compounds described herein and Z. J ack Hinz for
HPLC analysis.
Su p p or tin g In for m a tion Ava ila ble: The 1H, 13C, and
selected COSY spectra of the compounds in the Experimental
Section, and a molecular thermal ellipsoid plot of 7 (23 pages).
This material is contained in libraries on microfiche, im-
mediately follows this article in the microfilm version of the
journal, and can be ordered from the ACS; see any current
masthead page for ordering information.
1670, 1650, 1600, 1330, 1300, 1160, 1130 cm-1
. Anal. Calcd
for C19H14O4S: C, 67.44; H, 4.17; S, 9.47. Found: C, 67.31; H,
4.22; S, 9.77.
1,4-Dih yd r o-6-p h e n yl-7-(t olu e n e su lfon yl)-1,4-m e t h a -
n on a p h th a len e-5,8-d iol (6) a n d 1,4,8a -tr ih yd r o-6-p h en yl-
4a-(tolu en esu lfon yl)-1,4-m eth an on aph th alen e-5,8-dion e (7).
p-Toluenesulfinic acid (6.248 g, 0.04 mol) and 1,4-dihydro-6-
phenyl-1,4-methanonaphthalene-5,8-dione (5) (4.965 g, 0.02 mol)
J O9520856