Di-1-naphthylcarbene-Dibenzofluorene Rearrangement
J . Org. Chem., Vol. 63, No. 23, 1998 8421
data points in F2. C-13 decoupling was applied during
acquisition. A total of 987 increments in F1 were applied, 90°
phase-shifted sine bell squared window functions were applied
in both dimensions before transformation, and the matrix was
zero filled to 512 points in F2 and 1024 points in F1. An 1H-
13C HMBC19 magnitude mode experiment was obtained for 22
using conditions as for the HSQC except that the C-13 spectral
width was 11 900 Hz and 64 scans were acquired for each of
the 1024 increments in F1. The delay for evolution of long-
range couplings was optimized for J ) 6 Hz (83 ms).
GC-MS analyses were made on a Hewlett-Packard quad-
rupole mass-selective detector 5970 connected to a gas chro-
matograph equipped with a BP-5 capillary column (30 m ×
0.25 mm with 0.25 m phase thickness; He carrier at 20 psi
head pressure; injector, 200 °C; detector 280 °C; column
temperature, 100-250 °C, programmed at 16 °C/min). Iden-
tification of known compounds by 1H NMR and GC-MS
analysis of mixtures was done by direct comparison with
authentic samples. Melting points are uncorrected. Column
chromatography was performed using neutral Al2O3 (activity
I) unless otherwise stated. Di(1-naphthyl) ketone (19)20 and
di(1-naphthyl)carbinol20 (14) were synthesized according to
literature procedures.
) 8.3, 2H, H6,7), 7.90-7.94 (m, 4H, H4,5,8,9), 7.57 (ddd, J )
8.2, 6.9, 1.1, 2H, H2,11), 7.47 (ddd, J ) 8.1, 6.9, 1.2, 2H, H3,
10) 4.47 (s, 2H, H13,13′) (assignments are based on 2D
homonuclear 1H-1H coupling (COSY) experiments and differ
from those given in ref 9; in particular, an epi coupling15
between H-5,8 and H-1,12 was observed, which allowed the
assignment of the rest of the proton signals. The 2D spectrum
is shown in the Supporting Information); 13C NMR δ 139.9
(s), 139.8 (s), 132.7 (s), 130.7 (s), 129.0 (d), 127.8 (d), 126.5 (d),
125.2 (d), 124.0 (d), 118.7 (d), 34.4 (t); GC-MS retention time
23.6 min.
Tetr a (1-n a p h th yl)eth a n e (24) was prepared according to
the literature23 from di(1-naphthyl)chloromethane in 93%
yield: mp 282-285 °C (lit.20a mp 285-286 °C); 1H NMR δ 7.94
(d, J ) 8.4 Hz, 4 H) 7.59 (d, J ) 7.2 Hz, 4 H), 7.54 (d, J ) 8.0
Hz, 4 H), 7.44 (d, J ) 8.1 Hz, 4 H) 7.09-7.21 (m, 12 H), 6.65
(s, 2 H); 13C NMR δ 139.5 (s), 133.5 (s), 131.8 (s), 128.33 (d),
128.28 (d), 127.1 (d), 126.8 (d), 125.5 (d), 124.9 (d), 124.7 (d),
123.0 (d), 45.9 (d).
13,13′-Bis(d ib en zo[a ,i]flu or en yl) (23). A mixture of
dibenzo[a,i]fluorene (11) (0.136 g, 0.511 mmol) and dibenzoyl
peroxide (0.078 g, 0.32 mmol) was refluxed in 15 mL of dry
benzene for 2.5 d. More dibenzoyl peroxide (0.075 g, 0.31
mmol) was added, and the mixture was refluxed for another
2.5 d. The solvent was removed to give a brown residue, which
was washed with a small amount of acetone. The off-white
solid was then dissolved in a minimum amount of boiling
benzene. The fine white solid that separated upon cooling was
recovered by filtration. This afforded 44 mg (32%) of 23: mp
upon fast heating in an open capillary: the solid turned brown
at 320-325 °C and melted at 340-341 °C (lit.7b mp 338-350
Di(1-n a p h th yl) Keton e Hyd r a zon e. Standard proce-
dures21 for hydrazone preparation were modified as follows.
Di(1-naphthyl) ketone20 (19) (0.20 g, 0.71 mmol) was dissolved
in 5 mL of dry n-butanol; 1.0 mL of anhydrous hydrazine was
added to the solution, which was then refluxed under N2. After
both the second and the third day of reflux, 1.5 g of anhyd
MgSO4 and 0.5 mL of anhyd hydrazine were added to the
mixture. According to GC-MS analysis, complete conversion
to the hydrazone was achieved after 6 d of reflux. The hot
solution was filtered to remove MgSO4, and the solid was
washed with hot ethanol. After concentration and cooling, 0.15
g (71%) of the hydrazone was obtained: mp 147-149 °C (lit.6
1
°C, lit.24 mp 353-355 °C); H NMR (CDCl3, 27 °C) δ 7.0-8.2
1
(unresolved broad band) 5.88 (s); H NMR (CDCl2CDCl2, 131
°C) δ 7.83 (d, J ) 8.3 Hz, 4 H), 7.69 (d, J ) 8.3 Hz, 4 H), 7.3-
7.4 (br m, 12 H), 7.23 (br t, 4 H), 5.94 (s, 2 H); 13C NMR (CDCl3,
27 °C) δ 141.6, 130.4, 123-125 (br signal), 51.6; 13C NMR
(CDCl2CDCl2, 131 °C) δ 141.9, 140.2, 133.3, 130.8, 129.0, 128.6,
125.8, 124.6, 124.3, 118.1, 52.0.
Rea ction of Di(1-n a p h th yl)ca r bin ol (14) w ith An h y-
d r ou s P h osp h or ic Acid . This reaction6,7 was performed as
follows.
(a) A 0.50 g (1.8 mmol) portion of the carbinol 14 and 1.5 g
of crystalline H3PO4 were ground together. The paste was
transferred to a round-bottomed flask, which was evacuated
at 1-2 mbar. The flask was placed in an oil bath at 160 °C
for 1 h. The resulting solid was crushed to a powder, washed
with distilled H2O, and taken up in benzene. The organic
phase was washed with H2O until the water washings were
neutral. The benzene phase was dried with anhyd MgSO4 and
then concentrated to give 0.45 g of crude reaction mixture.
Column chromatography (hexane-benzene 10:1, changed
gradually to 1:1) afforded the following compounds:
Di(1-n a p h th yl)m eth a n e (18) as the first fraction: 0.02 g
(4%) of as white needles: mp 108-109 °C (lit.20b mp 107-108
°C); 1H NMR (200 MHz) δ 8.0 (m, 2 H), 7.9 (m, 2 H), 7.8 (d, J
) 8.2 Hz, 2 H), 7.5 (m, 4 H), 7.4 (dd, J ) 8.1, 7.1 Hz, 2 H), 7.1
(d, J ) 7.0 Hz, 2 H), 4.9 (s, 2H); 13C NMR (50 MHz) δ 136.1
(s), 133.8 (s), 132.2 (s), 128.7 (d), 127.1 (d), 127.0 (d), 126.1
(d), 125.6 (d), 125.6 (d), 123.9 (d), 35.7 (t).
1
mp 148 °C); H NMR (200 MHz) δ 8.9 (d, J ) 6.8 Hz, 1 H),
7.8-7.9 (m, 4 H), 7.7 (dd, J ) 7.5, 1.6 Hz, 1 H), 7.4-7.6 (m, 6
H), 7.2-7.3 (m, 2 H), 5.3 (s, 2 H); 13C NMR (50 MHz) δ 148.7
(s), 135.6 (s), 134.3 (s), 133.8 (s), 132.4 (s), 131.1 (s), 129.9 (s),
129.5 (d), 128.9 (d), 128.7 (d), 128.4 (d), 127.8 (d), 127.3 (d),
127.1 (d), 126.7 (d), 126.6 (d), 126.4 (d), 125.9 (d), 125.8 (d),
125.4 (d), 124.8 (d).
Di(1-n a p h th yl)d ia zom eth a n e (9). To a solution of 0.18
g (0.61 mmol) of di(1-naphthyl) ketone hydrazone in 10 mL of
dry ether were added 0.30 g of anhyd Na2SO4, 0.5 mL of a
saturated ethanolic potassium hydroxyde solution, and 0.90
g of yellow HgO. The flask was cooled in an ice bath, and the
mixture was stirred in the dark for 10 h. After filtration, the
solvent was removed on a rotary evaporator, and the bright
red residue was dissolved in hexane. Upon cooling, 0.17 g
(95%) of 9 was obtained as red crystals: mp 75-80 °C dec (lit.22
mp 75 °C dec); 1H NMR δ 7.88-7.92 (m, 4 H), 7.80 (d, J ) 8.2
Hz, 2 H), 7.50 (ddd, J ) 8.2, 6.9, 1.2 Hz, 2 H), 7.44 (t, J A ) J B
) 7.7 Hz, 2H), 7.41 (ddd, J ) 8.4, 6.9, 1.4 Hz, 2 H), 7.37 (dd,
J ) 7.2, 1.2 Hz, 2 H); 13C NMR δ 134.5 (s), 130.6 (s), 128.9 (d),
128.7 (s), 127.8 (d), 126.4 (d), 126.3 (d), 126.1 (d), 125.8 (d),
124.8 (d), 58.3 (s).
Diben zo[c,g]flu or en e (12):9 mp 141-143 °C (lit.9 mp
142.5-143 °C); 1H NMR δ 8.76 (dd, J ) 8.4, 0.6 Hz, 2H), 7.99
(dd, J ) 8.0, 1.6 Hz, 2H), 7.87 (d, J ) 8.1 Hz, 2H), 7.73 (d, J
) 8.1, 2H), 7.5-7.6 (m, 4H), 4.11 (s, 2H); 13C NMR δ 142.9 (s),
138.3 (s), 133.9 (s), 128.8 (s), 128.7 (d), 127.7 (d), 126.7 (d),
124.8 (d), 124.7 (d), 122.8 (d), 38.9 (t); GC-MS retention time
21.7 min.
Diben zo[a ,i]flu or en e (11) as the second fraction: 0.16 g
(34%) of as white platelets; mp 233-234 °C; identified by NMR
and GC-MS comparison with the sample described above.
13H-13-[Di(1-n aph th yl)m eth yl]diben zo[a ,i]flu or en e (22)
as the third fraction: 0.23 g (49%); mp > 260 °C dec in open
Diben zo[a ,i]flu or en e (11):9 mp 232-233 °C (lit.9 mp 231-
233 °C); 1H NMR δ 8.12 (d, J ) 8.3 Hz, 2H, H1,12), 7.98 (d, J
1
capillary with fast heating; H NMR (CD2Cl2) δ 8.09 (d, J )
8.4 Hz, 2 H, H8′′,8′′′), 7.87 (d, J ) 8.3 Hz, 2 H, H6,7), 7.81 (d,
J ) 8.4 Hz, 2 H, H5,8), 7.75-7.78 (m, 4 H, H4,9,5′′,5′′′), 7.59
(d, J ) 8.2 Hz, 2 H, H4′′,4′′′), 7.55 (d, J ) 8.5 Hz, 2 H, H1,12),
7.38 (ddd, J ) 8.0, 6.8, 1.2 Hz, 2 H, H6′′,H6′′′), 7.33 (ddd, J )
8.4, 6.8, 1.6 Hz, 2 H, H7′′,H7′′′), 7.26 (ddd, J ) 8.1, 6.8, 1.2
Hz, 2 H, H3,10), 7.08-7.15 (m, 5 H, H1′,2,11,2′′,2′′′), 7.01 (t,
(19) Bax, A.; Summers, M. F. J . Am. Chem. Soc. 1986, 108, 2093-
2094.
(20) (a) Schmidlin, J .; Massini, P. Ber. Dtsch. Chem. Ges. 1909, 42,
2377-2392. (b) Blicke, F. F. J . Am. Chem. Soc. 1927, 49, 2843-2849.
(21) (a) Scho¨nberg, A.; Fateen, A. E. K.; Sammour, A. E. M. A. J .
Am. Chem. Soc. 1957, 79, 6020-6023. (b) Baltzly, R.; Mehta, N. B.;
Russell, P. B.; Brooks, R. E.; Grivsky, E. M.; Steinberg, A. M. J . Org.
Chem. 1961, 26, 3669-3676.
(23) Reimlinger. H.; Golstein, J .-P.; J adot, J .; J ung, P. Chem. Ber.
1964, 97, 349-362.
(24) Wanscheidt, A. Ber. Dtsch. Chem. Ges. 1926, 59, 2092-2100.
(22) Reimlinger, H. Chem. Ber. 1964, 97, 3493-3502.