Nelsen et al.
aqueous NaOH was added at ice-water bath temperature, and the
mixture was filtered and washed with brine. The solid was dispersed
into water, and excess 40% aqueous sodium hydroxide was added.
The mixture was filtered, washed with water, and dried to give
after removal of solvent, the solid was recrystallized from ethanol,
giving 18.2 g (91%) of white dibenzothiophene-9-oxide (mp: 187-
188 °C, lit.23 187-189 °C). H NMR (CDCl
1
) δ 7.48-7.59 (m,
3
6H), -7.8 (m, 2H). A solution of 3 g (15 mmol) of this material in
70 mL of concentrated sulfuric acid was cooled to 6-12 °C, and
60 mL of concentrated nitric acid was added slowly so that the
reaction temperature remained at 10-15 °C. The mixture was left
at this temperature for 30 min and then allowed to come to room
temperature over 30 min. The precipitate obtained by pouring the
nitration mixture on ice was washed with water and air-dried to
give 3.3 g (76%) of 3,7-dinitrodibenzothiophene-5-oxide as pale
0
1
.23 g (78.7%) of 2,7-diamino-9,10-dihydrophenanthrene (mp:
55-156 °C). The empirical formula C14 was established by
14 2
H N
high-resolution MS.
,7-Bis(9,9-azabicyclo[3.3.1]nonane-3-one)-9,10-dihydrophenan-
threne (BZ([CH )). A mixture of 3,7-diaminodibenzothiophene
0.23 g, 1.1 mmol), 2,7-cyclooctadieneone (0.3 g, 2.4 mmol), and
0 mL of CH OH was stirred for about one week at room
2
2 2
]
(
1
3
2
4
1
temperature. The solid that formed was filtered, and the portion
yellow crystals (mp: 257-258 °C, lit. 257-258 °C). H NMR
soluble in THF/ethanol was recrystallized from THF/methanol,
(CDCl
3
) δ 8.87 (d, J ) 2.1 Hz), 8.61 (dd, J ) 2.1 Hz, J ) 8.6
1
giving 0.31 g (63%) of (BZ([CH
CDCl
Hz, 2H), 6.80 (d, J ) 2.1 Hz, 4H), 4.55 (s, 4H), 3.4 (s, 4H), 2.68
dd, 4H), δ 2.42 (d, 4H), 1.6-2.0 (m,12H). The empirical formula
was established by MS.
,7-Bis(9,9-azabicyclo[3.3.1]nonane-3-one)fluorenone (BZ-
2
]
2
)) (mp: 280-281 °C). H NMR
2H), 8.12 (d, J ) 8.6 Hz).
(
3
) δ 7.51 (d, J ) 8.1 Hz, 2H), 6.91 (dd, J ) 8.1 Hz, J ) 2.1
3,7-Bis(9,9-azabicyclo[3.3.1]nonane-3-one)dibenzothiophene
(BZ(S)). A solution of 14.5 g (63 mmol) of stannous chloride
dihydrate in 21 mL of concentrated hydrochloric acid was added
to a hot solution (70-80 °C) of 1.66 g (5.8 mmol) of 3,7-
dinitrodibenzothiophene-5-oxide in 30 mL of acetic acid and stirred
for 2 h at room temperature. Then, the white suspension was heated
at 100 °C and stirred for 1 h. After cooling to room temperature,
the reaction mixture was filtered and washed with brine. The solid
was dispersed into water, and excess 40% aqueous sodium
hydroxide was added. The mixture was filtered, washed with water,
and dried to give 1 g (81.6%) of 3,7-diaminodibenzothiophene as
a pale yellow solid (mp: 172-173 °C, lit.23 172-173 °C). H NMR
(
30 34 2 2
C H N O
2
(CO)). 2,7-Diaminofluorenone (0.85 g, 4.1 mol), 2,6-cyclooctanone
(1.1 g, 0.9 mmol), and 40 mL of ethanol were refluxed about one
week. After filtration, the solid that formed was extracted with THF,
and the residue after evaporation was recrystallized from methanol/
1
ether, giving 0.5 g (9%) of BZ(CO) (mp: 282-283 °C). H NMR
(
6
2
3
CDCl ) δ 7.28 (d, J ) 8.5 Hz, 2H), 7.24 (d, J ) 2.7 Hz, 2H),
1
.96 (dd, J ) 8.5 Hz, J ) 2.7 Hz, 2H), 4.5 (s, 4H), 2.68, (dd, 4H),
.42 (d, 4H), 1.6-2.0 (m, 12H). The empirical formula C29
H N O
30 2 3
(CDCl ) δ 7.75 (d, J ) 8.5 Hz, 4H), 7.06 (d, J ) 2.2 Hz, 4H),
3
was established by MS.
6.77 (dd, J ) 8.5 Hz, J ) 2.2 Hz). A mixture of this material (0.86
2
,7-Dinitro-N-methylcarbazole. To a solution of 0.5 g of 2,7-
g, 4 mmol), 2,7-cyclooctadienone (1.1 g, 9 mmol), and 20 mL of
methanol was stirred about one week at room temperature. The
solid was filtered, and the portion soluble in THF/ethanol was
recrystallized several times from THF/methanol, giving 1.1 g (60%)
22
dinitrocarbazole in 10 mL of acetone was added 0.5 g of KOH
in 0.25 mL of water, and the reaction mixture was stirred at 50 °C
for 20 min. When the reddish solution of the potassium salt of 2,7-
dinitrocarbazole was obtained, dimethyl sulfate (1 mL, 8 mmol)
was added. After stirring at 50 °C for another 20 min, the reaction
mixture was cooled, diluted with water, and filtered. The solid was
1
of BZ(S) (mp: 307-308 °C). H NMR (CDCl ) δ 7.91 (d, 8.8
3
Hz, 4H), 7.38 (d, J ) 2.3 Hz, 4H), 7.12 (dd, J ) 8.8 Hz, J ) 2.3
Hz), 4.55 (s, 4H), 2.68, (dd, 4H), 2.42 (d, 4H), 1.6-2.0 (m,12H).
The empirical formula C H N O S was established by MS.
washed with water and dried in air, giving 0.51 g of 2,7-dinitro-
28
30
2
2
1
N-methylcarbazole (mp: 160-161 °C). H NMR (CDCl
3
) δ 8.44
2,7-Dinitrodibenzothiophene Sulfone. A solution of 50 g of
(
d, J ) 1.7 Hz, 2H), 8.26 (d, J ) 8.6 Hz, 2H), 8.22 (dd, J ) 8.6
Hz, J ) 1.7 Hz), 4.05 (s, 4H).
,7-Diamino-N-methylcarbazole. A solution of 2.1 g of SnCl
O in 1.5 mL of HCl was added dropwise to a hot solution (70-
0 °C) of 0.29 g (1.1 mmol) of 2,7-dinitro-N-methylcarbazole in 3
7
7% m-chloroperbenzoic acid (38.5 g, 0.22 mol) in 200 mL of
chloroform was slowly added to a solution of 18.4 g of diben-
zothiophene (0.1 mol) in 250 mL of chloroform at room temper-
ature, and the mixture was refluxed for 3 h. After the mixture
cooled, aqueous sodium bicarbonate was added and the acid was
dissolved. The chloroform solution was washed twice with saturated
2
2
‚
H
2
8
mL of acetic acid. After refluxing for 3 h, solvent was evaporated
and aqueous sodium hydroxide was added slowly, with cooling in
an ice bath. After stirring for 0.5 h, the product was filtered, washed
with water several times, and dried in air to give 0.2 g (90%) of
3 2 4
NaHCO , dried over Na SO , and concentrated. Recrystallization
from ethanol gave 19.6 g (91%) of dibenzothiophene sulfone as a
25
white solid (mp: 232-233 °C, lit. 232-234 °C). A solution of
2
,7-diamino-N-methylcarbazole (mp: 168-169 °C). 1H NMR
4
g (15 mmol) of dibenzothiophene sulfone in 70 mL of
(
CDCl
dd, J ) 8.2 Hz, J ) 1.4 Hz), 3.79 (s, 4H), 3.65 (s, 3H).
,7-Bis(9,9-azabicyclo[3.3.1]nonane-3-one)-N-methylcarba-
3
) δ7.70 (d, J ) 8.2 Hz, 2H), 6.63 (d, J ) 1.4 Hz, 2H), 6.59
concentrated sulfuric acid was cooled to 6-12 °C, and 60 mL of
concentrated nitric acid was added slowly so that the reaction
temperature remained at 10-15 °C. The mixture was left at this
temperature for 30 min and then allowed to come to room
temperature over 30 min. After the mixture stirred at room
temperature for 12 h, the precipitate was obtained by pouring the
nitration mixture on ice and was collected on a Buchner funnel,
washed with water, and air-dried to give 3.5 g (55%) of 3,7-
dinitrodibenzothiophene sulfone as pale yellow crystals (mp: 253-
(
2
zole (BZ(NMe)). A mixture of 2,7-diamino-N-methylcarbazole (0.2
g, 0.9 mmol), 2,7-cyclooctadieneone (0.3 g, 2.4 mmol), and 20 mL
of methanol was stirred for about one week at room temperature.
After filtration, the portion soluble in THF/ethanol was crystallized
from THF/methanol to give 0.25 g (60%) of BZ(NMe) (mp: 303-
1
3
04 °C). H NMR (CDCl
3
) δ 7.82 (d, J ) 8.6 Hz, 2H), 6.87 (dd,
J ) 8.5 Hz, J ) 2.1, 2H), 6.84 (d, J ) 2.1 Hz, 2H), 4.60 (s, 4H),
.74 (s, 3H), 2.68 (dd, 4H), 2.42 (d, 4H), 1.6-2.0 (m, 12H). The
empirical formula C29 was established by MS.
,7-Dinitrodibenzothiophene-5-oxide. A solution of 23 g of
7% m-chloroperbenzoic acid (17.3 g, 0.1 mol) in 200 mL of
24
1
2
54 °C, lit. 257-258 °C). H NMR (CDCl
Hz, 2H), 8.6 (dd, J ) 2.1 Hz, J ) 8.4, 2H), 8.12 (d, J ) 8.4 Hz,
H).
,7-Bis(9,9-azabicyclo[3.3.1]nonane-3-one)dibenzothiophene
Sulfone (BZ(SO )). A solution of 10 g (45 mmol) of stannous
3
) δ 8.77 (d, J ) 2.1
3
33 3 2
H N O
2
3
3
7
2
chloroform was slowly added to a solution of 18.4 g of diben-
zothiophene (0.1 mol) in 250 mL of chloroform at -30 to -35
chloride dihydrate in 8 mL of concentrated hydrochloric acid was
added to a hot solution (70-80 °C) of 1.6 g (5 mmol) of 3,7-
°
C. After stirring at -30 °C for 1 h, the mixture was stirred at
room temperature for 1 h. Aqueous Na
into the mixure until the acid dissolved. The organic layer was
washed twice with saturated NaHCO and dried over Na SO , and
2 3
CO was added dropwise
(
23) LaRochelle, R. W.; Trost, B. M. J. Am. Chem. Soc. 1971, 93, 6077-
6
086.
3
2
4
(24) Brown, R. K.; Nelson, N. A.; Wood, J. C. J. Am. Chem. Soc. 1952,
7
4, 1165-1167.
(22) Morin, J.-F.; Leclerc, M. Macromolecules 2001, 34, 4680-4682.
(25) LaCount, R. B.; Friedman, S. J. Org. Chem. 1977, 42, 2751-2754.
4294 J. Org. Chem., Vol. 71, No. 11, 2006