Diindeno[1,2,3,4-defg;1′,2′,3′,4′-mnop]chrysene
-Bromo-9-fluorenone (8). A solution of 5.0 g (22 mmol) of 10
and 7.75 g (33.4 mmol) of red mercuric oxide in 100 mL of carbon
tetrachloride was heated to reflux for 30 min. Bromine (1.8 mL, 34
mmol) was then added slowly, and the solution was irradiated with a
A R T I C L E S
1
2H, J ) 8.0 and 0.8 Hz), 7.41 (d, 2H, J ) 7.6 Hz), 7.31-7.17 (m,
6H); characteristic of minor isomer, 8.37 (d, 2H, J ) 7.6 Hz). UV
) λmax (log ꢀ): 476 (4.3), 388 (3.8), 284 sh (4.6), 266 (4.7), 254
(4.7), 244 nm sh (4.7). MS (EI, 70 eV) m/z (rel intensity): 488 (13,
(CHCl
3
+
81
+
81
79
+ 79
2
50 W tungsten lamp for 3.5 h. After the solution was allowed to cool
M , Br
2
), 486 (23, M , Br Br), 484 (14, M , Br
2
), 406 (2, [M -
+
81
+
79
+
to room temperature, the mercury salts were filtered out and washed
with dichloromethane. The filtrate was washed with 10% sodium
bisulfite solution, saturated sodium bicarbonate solution, and water (2
Br] , Br), 404 (2, [M - Br] , Br), 326 (100, [M - 2Br] ), 162
+
(22). HRMS (EI, 70 eV): calcd for C26
483.9459.
H12Br
2
(M ) 483.9462, found
×
75 mL portions of each) and dried over MgSO
4
. Evaporation of the
Diindeno[1,2,3,4-defg;1′,2′,3′,4′-mnop]chrysene (1). A 100 mg
(0.206 mmol) sample of 2 was pyrolyzed under reduced pressure from
a bed of quartz chips with a nitrogen bleed as described previously in
detail.6a With the oven at 1050 °C and a pressure of 0.8-1.0 mmHg,
the pyrolysis took 20 min. The crude pyrolysate (65% mass recovery)
was suspended in dichloromethane and filtered through a plug of silica
gel, flushing with dichloromethane. The C H bowl was isolated by
solvent under reduced pressure followed by chromatography of the
crude product on silica gel, using 10% ethyl acetate/hexane as eluant,
gave 3.65 g (63% yield) of 8. Fractional recrystallization from ethyl
20
acetate gives pure, thick, yellow needles: mp 136-138 °C (lit. 134.5-
1
1
7
35.0 °C). H NMR (400 MHz, CDCl
.53-7.48 (m, 3H), 7.42 (d, 1H, J ) 8.0 Hz), 7.36-7.30 (m, 2H). 13
): δ 191.29, 147.13, 142.52, 135.40, 134.99,
34.27, 134.07, 131.36, 129.88, 124.73, 120.63, 120.49, 119.46. IR
3
): δ 7.69 (d, 1H, J ) 7.4 Hz),
C
26
12
NMR (100 MHz, CDCl
1
3
chromatography on aluminum oxide with cyclohexane as the eluant
(see text). The product thus obtained was washed with acetone, giving
-
1
+
33
1
(
neat): 1722 cm . MS (EI, 70 eV) m/z (rel intensity): 260 (100, M ,
Br), 258 (100, M , Br), 232 (10, [M - CO] , Br), 230 (10, [M -
24.8 mg (37% yield) of 1 as a yellow powder: mp > 300 °C. H
81
+
79
+ 81
NMR (400 MHz, CDCl ): δ 8.26 (d, 4H, J ) 8.0 Hz), 7.86 (d, 4H, J
3
CO] , 79Br), 179 (5, [M - Br]+).
+
1
) 6.8 Hz), 7.62 (dd, 4H, J ) 8.0 Hz and J ) 7.2 Hz). H NMR (400
1
-Bromo-9-fluorenone Tosylhydrazone (11). A solution of 2.5 g
MHz, 423 K, C D NO ): δ 8.30 (d, 4H, J ) 8.1 Hz), 7.98 (d, 4H, J
6
5
2
) 7.1 Hz), 7.69 (t, 4H, J ) 7.6 Hz). 13C NMR (100 MHz, 423 K,
C D NO ): δ 142.38, 139.32, 137.31, 134.15, 129.62, 125.21, 123.16.
(9.7 mmol) of 8, a few drops of concentrated HCl, and 2.5 mL (23
mmol) of trimethyl orthoformate in 60 mL of dry methanol was heated
to reflux. Tosylhydrazide (1.7 g, 9.1 mmol) was added, and the solution
was heated to reflux for another 16 h. After the reaction mixture was
cooled to room temperature, the yellow precipitate was isolated by
filtration to give 3.8 g (93% yield) of pure 11. Recrystallization from
ethyl acetate gives shiny yellow plates: mp 185-190 °C (dec).
Unchanged 8 can be recovered from the filtrate by chromatography on
6
5
2
UV (CH Cl , from diode array detector of the HPLC) λ (A ): 402
2
2
max
rel
sh (1.0), 360 (4.3), 342 (3.5), 323 sh (6.6), 288 (10.3), 280 (17.9), 260
(18.6), 252 (14.6), 226 nm (16.0). MS (EI, 70 eV) m/z (rel intensity):
+
2+
324 (100, M ), 322 (18), 162 (10, M ). HRMS (EI, 70 eV): calcd
for C H 324.0937, found 324.0939.
26
12
Diindeno[5,6,7,1-defg;5′,6′,7′,1′-lmnop]chrysene (14). A 50 mg
(0.10 mmol) sample of 2 was pyrolyzed as above at 1200 °C. After
purification as above, approximately 1 mg (ca. 3% yield) of 14 was
1
silica gel with 10% ethyl acetate/hexane as the eluant. H NMR (400
MHz, CDCl
J ) 7.2 Hz), 7.68 (d, 1H, J ) 7.2 Hz), 7.55 (d, 1H, J ) 7.2 Hz), 7.48
t, 1H, J ) 7.6 Hz), 7.47 (d, 1H, J ) 8.4 Hz), 7.38 (t, 1H, J ) 7.6 Hz),
.33 (d, 2H, J ) 8.0 Hz), 7.19 (t, 1H, J ) 7.6 Hz), 2.24 (s, 3H). 13
NMR (100 MHz, DMSO-d ): δ 150.93, 143.81, 142.58, 139.23, 134.94,
33.57, 132.28, 131.77, 131.60, 129.21, 128.93, 128.87, 128.80, 127.93,
3
): δ 8.47 (s, 1H), 8.07 (d, 2H, J ) 8.4 Hz), 7.94 (d, 1H,
1
isolated as a yellow powder. H NMR (400 MHz, CDCl ): δ 9.02 (d,
3
(
7
2H, J ) 7.6 Hz), 8.44 (d, 2H, J ) 7.6 Hz), 8.43 (s, 2H), 8.08 (t, 2H,
13
C
J ) 7.6 Hz), 7.73 (d, 2H, J ) 5.2 Hz), 7.56 (d, 2H, J ) 5.2 Hz).
C
6
NMR (100 MHz, CDCl ): δ 142.7, 104.4, 89.6 (other signals too weak
3
1
1
to observe). UV (CH Cl , from diode array detector of the HPLC) λ
2
2
max
-
1
20.74, 119.72, 116.90, 21.10. IR (neat): 3425, 1642, 1166 cm . UV
rel
(A ): 510 (30), 484 (40), 448 (41), 414 sh (80), 384 (230), 370 (290),
(
2
4
CHCl
3
) λmax (log ꢀ): 338 (3.96), 324 (3.99), 266 (4.58), 258 (4.56),
350 (210), 348 sh (310), 338 (330), 322 (500), 310 (310), 298 (180),
288 (160), 284 sh (140), 248 nm (440). MS (EI, 70 eV) m/z (rel
+
46 nm sh (4.44). HRMS (EI, 70 eV): calcd for C20
26.0037, found 426.0035. Anal. Calcd for C20
H15BrN
2
2
O S (M )
+
2+
2 2
H15BrN O S: C, 56.22;
intensity): 324 (100, M ), 322 (16), 162 (10, M ). HRMS (EI, 70
eV): calcd for C H 324.0937, found 324.0942.
H, 3.54; N, 6.56. Found: C, 56.04; H, 3.49; N, 6.58.
E)- and (Z)-1,1′-Dibromobifluorenylidene (2). A solution of 2.00
26
12
(
Acknowledgment. This paper is dedicated to Professor T.
Ross Kelly on his 60th birthday. We thank Richard Staples for
the X-ray crystal structure of 1, Roy Shenhar for the 13C NMR
of 1, and Damian Slizys for the X-ray crystal structure of 2.
Financial support from the National Science Foundation is
gratefully acknowledged.
g (4.68 mmol) of 11 and 350 mg (6.48 mmol) of freshly prepared, dry
sodium methoxide in 55 mL of dry pyridine was heated at 110 °C for
45 min (until the reaction mixture bubbles vigorously and turns brown).
The mixture was diluted with 100 mL of water and extracted quickly
with 3 × 50 mL of dichloromethane. The organic layer was dried over
4
MgSO and evaporated quickly under reduced pressure with minimal
1
heating. The crude 1-bromo-9-diazofluorene (12) [ H NMR (300 MHz,
CDCl ): δ 7.89 (d, 1H, J ) 7.8 Hz), 7.84 (d, 1H, J ) 7.8 Hz), 7.43-
.28 (m, 4H), 7.13 (t, 1H, J ) 7.6 Hz). IR (neat): 2062 cm ] was
then dissolved quickly in 50 mL of dichloromethane, and approximately
0 mg of copper (I) bromide was added. The solution was heated to
3
Supporting Information Available: NMR and UV spectra
of compounds 1 and 14. Tables of data and several views of
the X-ray crystal structures of 1 and 2 (PDF). This material is
available free of charge via the Internet at http://pubs.acs.org.
-
1
7
2
reflux for 15 min. Evaporation of the solvent under reduced pressure
followed by chromatography on silica gel with 5% ethyl acetate/hexane
as the eluant gave 763 mg of 2 (67% yield). Recrystallization from
JA0123148
2
3
(33) Crystals were obtained for X-ray crystal analysis by first heating a solution
of 1 in DMF at reflux in an oil bath. The bath was then turned off but not
removed, and the solution was allowed to cool slowly overnight, giving 1
as fine needles.
acetone gave red crystals: mp of the isomer mixture 224-226 °C (lit.
1
230-231 °C). H NMR (400 MHz, CDCl
3
): δ major isomer, 7.73 (dd,
2
H, J ) 7.6 and 0.8 Hz), 7.66 (dd, 2H, J ) 7.6 and 0.8 Hz), 7.52 (dd,
J. AM. CHEM. SOC.
9
VOL. 124, NO. 30, 2002 8875