5254 J . Org. Chem., Vol. 61, No. 16, 1996
Rathore et al.
1391, 1208, 1040, 850, 787, 752, 695 cm-1; 1H NMR (CDCl3) δ
2.04 (s, 6H), 3.15 (s, 6H), 4.02 (s, 6H), 6.12 (s, 2H), 6.72 (s,
2H), 6.74 (s, 2H), 7.24 (dd, J ) 7.5 and 7.2 Hz, 2H), 7.36 (dd,
J ) 7.5 and 7.2 Hz, 2H), 7.71 (d, J ) 7.2 Hz, 2H), 7.85 (d, J )
7.5 Hz, 2H); GC-MS m/ z 512 (M+), 512 calcd for C32H32O6]
which was converted (with the same sequence of reactions as
described for the corresponding acenaphthylene 10) to 9,10-
bis(2,5-dimethoxy-4-methylphenyl)phenanthrene (11). Recrys-
tallization from isopropyl alcohol furnished pure 11 as an ivory
powder (1.00 g, 88% over three steps): mp 224-226 °C; IR
(KBr) 2931, 2826, 1504, 1462, 1398, 1208, 1047, 864, 758, 723,
632 cm-1; 1H NMR (CDCl3) δ 2.21 (s, 3H), 2.22 (s, 3H), 3.48 (s,
3H), 3.58 (s, 6H), 3.59 (s, 6H), 6.59 (s, 1H), 6.64 (s, 3H), 7.44-
7.63 (m, 6H), 8.77 (d, J ) 8.4 Hz, 2H); 13C NMR (CDCl3) 16.37,
16.41, 55.74, 55.84, 56.01, 113.13, 113.80, 115.56, 122.48,
126.01, 126.27, 126.32, 126.62, 127.46, 127.72, 129.97, 130.21,
131.85, 131.97, 134.51, 134.71, 150.89, 151.20, 151.48; GC-
MS m/ z 478 (M+), 478 calcd for C32H30O4. Anal. Calcd for
C32H30O4: C, 80.31; H, 6.32. Found: C, 79.64; H 6.25.
was treated with ethanol (1 mL) and hydrogen peroxide (30%,
1 mL). After stirring for 1 h, it was worked up in the usual
manner to afford the unreacted olefin 1 in a quantitative yield
(38 mg, 93%).
The various hydrogenation products listed below were
prepared using the general procedure described above and the
characteristic spectral data are given below.
2,3-Bis(2,5-d im et h oxy-4-m et h ylp h en yl)b icyclo[2.2.2]-
octa n e (1H2): mp 128-129 °C; IR (KBr) 2938, 2861, 1504,
1469, 1398, 1363, 1208, 1047, 871, 653 cm-1; 1H NMR (CDCl3)
δ 1.51-1.88 (m, 10H), 2.10 (s, 6H), 3.49 (s, 6H), 3.50 (s, 6H),
3.87 (br s, 2H), 6.42 (s, 2H), 6.49 (s, 2H); 13C NMR (CDCl3)
15.45, 21.58, 28.00, 28.67, 39.25, 55.61, 56.14, 112.15, 113.02,
123.23, 130.38, 150.53, 151.34; GC-MS m/ z 410 (M+), 410
calcd for C26H34O4. Anal. Calcd for C26H34O4: C, 76.06; H,
8.35. Found: C, 75.19; H, 8.35.
2,3-Bis(4-m eth oxyph en yl)bicyclo[2.2.2]octan e (2H2): mp
87-88 °C; 1H NMR (CDCl3) δ 1.44-1.94 (m, 10H), 3.55 (s, 2H),
3.69 (s, 6H), 6.60 (d, J ) 8.7 Hz, 4H), 6.83 (d, J ) 8.7 Hz, 4H);
13C NMR (CDCl3) 21.03, 27.82, 29.63, 45.54, 55.00, 112.66,
130.09, 135.33, 156.63; GC-MS m/ z 322 (M+), 322 calcd for
C22H26O2. Anal. Calcd for C22H26O2: C, 81.95; H, 8.13.
Found: C, 81.51; H, 7.98.
(E)-1-(2,5-Dim et h oxy-4-m et h ylp h en yl)-2-p en t a m et h -
ylp h en yleth en e (15). To a suspension of sodium hydride
(0.80 g, 60% dispersion in mineral oil, 20 mmol) in a mixture
of N,N-dimethylformamido-dichloromethane (2:1, 60 mL) at
0 °C, was added (pentamethylbenzyl)triphenylphosphonium
bromide [prepared by refluxing a solution of pentamethylben-
zyl bromide45 (5.59 g, 11.1 mmol) and triphenylphosphine (12
mmol) in toluene (50 mL) for 48 h] under an argon atmosphere.
After the mixture was stirred for 5 min, 2,5-dimethoxy-4-
methylbenzaldehyde46 (2.0 g, 11.1 mmol) was added in one
portion and the mixture was refluxed for 3 h. The usual
aqueous workup and evaporation of the solvent in vacuo
afforded a solid residue which upon chromatographic purifica-
tion on silica gel with 1:1 chloroform-hexanes mixture as
eluent and recrystallization from methanol afforded pure (E)-
stilbene 15 as colorless plates (1.78 g, 50%): mp 113-114 °C;
2,3-Bis(4-m eth ylp h en yl)bicyclo[2.2.2]octa n e (3H2): mp
74-75 °C; 1H NMR (CDCl3) δ 1.52 (br d, J ) 8.1 Hz, 2H), 1.77-
1.91 (m, 8H), 1.97 (br s, 2H), 2.22 (s, 6H), 3.04 (s, 2H), 6.84 (d,
J ) 8.4 Hz, 4H), 6.89 (d, J ) 8.4 Hz, 4H); 13C NMR (CDCl3)
20.88, 21.11, 27.88, 29.65, 45.97, 128.00, 129.05, 133.88,
140.17; GC-MS m/ z 290 (M+), 290 calcd for C22H26
. Anal.
Calcd for C22H26: C, 90.98; H, 9.02. Found: C, 90.42; H, 8.83.
2,3-Dip h en ylbicyclo[2.2.2]octa n e (4H2): mp 93-94 °C;
1H NMR (CDCl3) δ 1.55-1.97 (m, 8H), 2.08 (br s, 2H), 3.71 (s,
2H), 6.97-7.14 (m, 10H); 13C NMR (CDCl3) 21.06, 27.87, 29.42,
46.42, 124.69, 127.23, 129.21, 143.14; GC-MS m/ z 262 (M+),
262 calcd for C20H22. Anal. Calcd for C20H22: C, 91.55; H, 8.45.
Found: C, 90.97; H, 8.51.
IR (KBr) 2924, 1504, 1464, 1398, 1208, 1047, 977, 850 cm-1
;
1H NMR (CDCl3) δ 2.23 (s, 9H), 2.25 (s, 3H), 2.28 (s, 6H), 3.76
(s, 6H), 3.86 (s, 6H), 6.71 (d, J ) 16.8 Hz, 1H), 6.73 (s, 1H),
7.07 (s, 1H), 7.09 (d, J ) 16.8 Hz, 1H); 13C NMR (CDCl3) 16.33,
16.59, 16.77, 18.08, 56.10, 56.74, 108.76, 115.67, 125.28,
127.39, 129.10, 129.39, 132.11, 132.76, 133.89, 136.46, 151.39,
152.54; GC-MS m/ z 324 (M+), calcd for C22H28O2. Anal.
Calcd for C22H28O2: C, 81.44; H, 8.70. Found: C, 81.18; H,
8.59.
Bia d a m a n ta n e (5H2): mp 184-185 °C (lit.19 mp 184-185
°C) ; 1H NMR (CDCl3) δ 1.38-1.88 (m, 30 H); 13C NMR (CDCl3)
27.91, 28.08, 28.25, 31.66, 38.44, 39.63, 42.41; GC-MS m/ z
270 (M+), calcd for C20H30
.
2-(1,1-Dia n isylm eth yl)a d a m a n ta n e (6H2): mp 135-136
1
°C; H NMR (CDCl3) δ 1.42-1.91 (m, 15H), 2.41 (d, J ) 12.3
Hz, 1H), 3.75 (s, 6H), 6.82 (d, J ) 8.4 Hz, 4H), 7.23 (d, J ) 8.4
Hz, 4H); 13C NMR (CDCl3) 27.80, 28.04, 29.06, 31.25, 38.32,
39.29, 47.77, 51.34, 113.82, 128.59, 136.80, 157.60; GC-MS
m/ z 362 (M+), 362 calcd for C25H30O2. Anal. Calcd for
C25H30O2: C, 82.83; H, 8.34. Found: C, 82.48; H, 3.22.
1,1,2,2-Tetr akis(4-m eth oxyph en yl)eth an e (7H2): mp 188-
189 °C (lit.22 mp 189-190 °C) ; 1H NMR (CDCl3) δ 2.31 (s,
2H), 3.82 (s, 12H), 6.97 (d, J ) 8.4 Hz, 8H), 7.19 (d, J ) 8.4
Hz, 8H); 13C NMR (CDCl3) 49.30, 114.08, 129.27,137.05,
157.90; GC-MS m/ z 227 (M+ - 227), 227 calcd for C30H30O4 -
C15H15O2.
Hyd r ogen a tion of Olefin s w ith th e Bor a n e-Meth yl
Su lfid e (BMS) Com p lex in th e P r esen ce of Or a n ge
CRET+‚ in Dich lor om eth a n e. Gen er a l P r oced u r e. Solid
Orange CRET+‚ (0.67 g, 1.1 mmol) was added to a prechilled
(∼0 °C) solution of the olefin 1 (408 mg, 1.0 mmol) in
dichloromethane (20 mL), under an argon atmosphere. The
highly colored mixture was stirred, and the BMS complex (0.20
mL, 2.0 mmol) was added with the aid of a hypodermic syringe.
The highly colored solution was progressively bleached to
afford a pale yellow solution. The reaction mixture was
quenched with a saturated aqueous potassium carbonate
solution (20 mL) and diluted with dichloromethane (20 mL).
The organic layer was separated, washed with water (3 × 25
mL), and dried over anhydrous magnesium sulfate. Evapora-
tion of the solvent in vacuo afforded a solid residue which upon
GC and GC-MS analysis indicated that it consisted mainly
of reduced 2,3-diarylbicyclooctane 1H2 and neutral CRET
together with traces of unreacted bicyclooctene 1. Further
purification by flash chromatography on silica gel using
mixture of ether-hexanes (1:1) as eluent afforded the hydro-
genated product 1H2 in excellent yield (360 mg, 88%) together
with unreacted diarylbicyclooctene 1 (33 mg, 8%). [Note that
the neutral CRET (292 mg, 98%) was recovered quantita-
tively].
1,2-Bis(2,5-d im et h oxy-4-m et h ylp h en yl)cycloh exa n e
(8H2): mp 105-107 °C; IR (KBr) 2931, 2847, 1511, 1462, 1398,
1208, 1047, 857, 808, 681 cm-1; 1H NMR (CDCl3) δ 1.67-1.82
(m, 4H), 1.97-2.00 (m, 4H), 2.11 (s, 6H), 3.47 (s, 6H), 3.58 (s,
6H), 3.69 (dd, J ) 4.7 Hz, 2H), 6.48 (s, 2H), 6.59 (s, 2H); 13C
NMR (CDCl3) 15.84, 24.84, 29.03, 36.09, 56.11, 56.32, 112.38,
113.60, 123.73, 131.97, 150.82, 151.38; GC-MS m/ z 384 (M+),
384 calcd for C24H32O4. Anal. Calcd for C24H32O4: C, 74.97;
H, 8.39. Found: C, 74.64; H, 8.42.
1,2-Bis(2,5-d im et h oxy-4-m et h ylp h en yl)cyclop en t a n e
(9H2): mp 100 °C; IR (KBr) 2945, 2826, 1511, 1469, 1398, 1209,
1047, 864, 829, 681, 632 cm-1;1H NMR (CDCl3) δ 1.98-2.07
(m, 6H), 2.11 (s, 6H), 3.44 (s, 6H), 3.54 (s, 6H), 3.83 (dd, J )
4.8 Hz, 2H), 6.23 (s, 2H), 6.44 (s, 2H); 13C NMR (CDCl3) 15.87,
24.00, 30.72, 41.71, 56.00, 111.38, 113.22, 123.83, 129.84,
150.83, 151.43; GC-MS m/ z 370 (M+), 370 calcd for C23H30O4.
Anal. Calcd for C23H30O4: C, 74.56; H, 8.16. Found: C, 74.51;
H, 8.10.
In a control experiment, a solution of olefin 1 (41 mg, 0.1
mmol) in dichloromethane (2 mL) was treated with excess
BMS complex (0.02 mL, 0.2 mmol) under an argon atmosphere
at 0 °C. The reaction mixture was stirred for 3 h at 0 °C and
was further refluxed overnight. The cooled reaction mixture
1,2-Bis(2,5-d im et h oxy-4-m et h ylp h en yl)-1,2-d ih yd r o-
a cen a p h th ylen e (10H2): mp 124-125 °C; IR (KBr) 2995,
2931, 2826, 1511, 1462, 1398, 1208, 1047, 857, 829, 787, 660
cm-1 1H NMR (CDCl3) δ 2.07 (s, 6H), 3.27 (s, 6H), 3.58 (s,
;
(45) Longone, D. T.; Simanyi, L. H. J . Org. Chem. 1964, 29, 3245.
(46) Staab, H. A.; Herz, C. P.; Henke, H. E. Chem. Ber. 1977, 110,
3351.
6H), 5.69 (s, 2H), 5.93 (br s, 2H), 6.43 (s, 2H), 7.15 (d, J ) 6.9
Hz, 2H), 7.51 (dd, J ) 8.1 and 6.9 Hz, 2H), 7.71 (d, J ) 8.1