A. Sygula et al. / Tetrahedron 57 %2001) 3637±3644
3643
1
04.79, 104.64, 101.84, 101.71, 0.45. MS ꢀEI, 70 eV) m/z,
rel. intensity) 636 ꢀ18), 635 ꢀ40), 634 ꢀ100), 633 ꢀ71), 630
replaced with styrene. Chromatography of the crude product
ꢀsilica gel, DCM) provided 140mg ꢀ45%) of dark solid, mp
ꢀ
ꢀ
1
238±2408C. H NMR ꢀ300 MHz, CDCl ) d 8.74 ꢀs, 2H),
10), 618 ꢀ22), 531 ꢀ21). HRMS ꢀEI, 70 eV) calcd for
3
1
C H Si ꢀM ) 634.2364, found 634.2375.
4
8.70ꢀs, 2H), 8.38 ꢀs, 2H), 8.30ꢀd, J8.7 Hz, 2H), 8.00 ꢀd,
0
42
4
1
3
J8.7 Hz, 2H), 7.31±7.36 ꢀm, 20H). C NMR ꢀ75.4 MHz,
4
ꢀ
4
.1.7. 1,2,5,6-Tetraphenylcorannulene ꢀ17). 600 mg
1.06 mmol) 7, 670mg ꢀ5.3 mmol) phenylboronic acid,
2 mg ꢀ0.035 mmol) PdꢀPPh3)4 and 1.66 g of Na CO
CDCl ) d 141.64, 141.62, 140.10, 140.01, 136.34, 135.19,
3
134.78, 132.57, 132.51, 130.64, 130.36, 129.10, 129.06,
128.75, 128.59, 128.31, 127.87, 127.38, 127.31, 127.06,
126.92, 124.93, 124.58. HRMS ꢀEI, 70eV) calcd for
2
3
were re¯uxed for 24 h in a solvent mixture of toluene
50ml), ethanol ꢀ50ml) and water ꢀ20ml). The solvents
1
ꢀ
C H ꢀM ) 654.2348, found 654.2356.
5
2
30
were removed under reduced pressure and the solid residue
was treated with water, extracted with DCM, and the
extracts dried ꢀmagnesium sulfate) and evaporated. The
resulting crude material was crystallized from n-butanol/
4.1.11. 1,2,5,6-Tetrakisꢀbromomethyl)corannulene ꢀ22).
110mg of 15 ꢀ0.36 mol) was re¯uxed and irradiated for
6 h with a sun lamp with 260mg ꢀ1.44 mmol) of NBS and
1
toluene to give 388 mg of 17 ꢀ66%), mp 311±3128C. H
NMR ꢀ400 MHz, CDCl ): d 7.80ꢀd, J8.8 Hz, 2H), 7.61
10mg of dibenzoyl peroxide in 30ml of CCl . The solvent
4
was removed, the residue taken into DCM, washed well
with water, dried ꢀmagnesium sulfate) and evaporated.
Crystallization from toluene±ethanol provided 153 mg
3
1
3
ꢀ
d, J8.8 Hz, 2H), 7.58 ꢀs, 2H), 7.24±7.30ꢀm, 2 0H ).
C
NMR ꢀ75.4 MHz, CDCl ) d 139.16, 138.86, 138.62, 138.57,
3
1
1
1
35.47, 135.23, 134.24, 131.72, 131.71, 130.79, 130.59,
30.21, 127.79, 127.77, 127.47, 127.40, 126.89, 126.85.
ꢀ68%) of 22, mp 274±2768C. H NMR ꢀ400 MHz,
CDCl ): d 8.07 ꢀs, 2H), 8.00 ꢀd, J8.7 Hz, 2H), 7.89 ꢀd,
3
1
13
J8.7 Hz, 2H), 5.18 ꢀs, 4H), 5.15 ꢀs, 4H). C NMR
HRMS ꢀEI, 70eV) calcd for C 44H26 ꢀM ) 554.2035,
found 554.2040.
ꢀ75.4 MHz, CDCl ) d 136.07, 135.46, 135.45, 135.19,
3
1
34.85, 129.77, 129.74, 128.30, 125.40, 125.27, 25.31.
1
4
.1.8. 1,2,5,6-Tetrakisꢀ2-methoxycarbonylethenyl)cor-
HRMS ꢀEI, 70eV) calcd for C 24H Br ꢀM ) 621.7788,
14 4
annulene ꢀ19). Methyl acrylate ꢀ820mg, 9.56 mmol) was
added under argon to a suspension of 14 ꢀ350mg,
found 621.7799.
0
o-tolylphosphine ꢀ29 mg, 0.05 mmol), potassium carbonate
.46 mmol), palladiumꢀII) acetate ꢀ11 mg, 0.05 mmol), tri-
4.1.12. Adduct 23. A mixture of 22 ꢀ155 mg, 0.25 mmol),
maleic anhydride ꢀ490mg, 5 mmol), potassium iodide
ꢀ270mg, 1.62 mmol) and dry 18-crown-6 ꢀ264 mg,
1 mmol) in 25 mL of dry toluene was re¯uxed for 20h.
The reaction mixture was washed with aqueous sodium
thiosulfate, then water, and dried ꢀmagnesium sulfate).
The puri®cation of the residue by column chromatography
on silica gel with DCM as eluent afforded 23 as a yellow
ꢀ
ꢀ
660mg, 4.6 mmol) and tetrabutylammonium bromide
620mg, 1.84 mmol) in 10ml of DMF. The mixture was
stirred at 95±1008C for 48 h, cooled to room temperature,
diluted with 30ml of DCM and ®ltered. The organic layer
was washed three times with water, dried ꢀmagnesium sul-
fate) and evaporated. The crude material was puri®ed by
chromatography on silica gel with DCM/ethyl acetate
1
solid ꢀ28 mg, 23%). H NMR ꢀ300 MHz, CDCl3) d 7.95 ꢀs,
2H), 7.92 ꢀd, 2H, J9.0Hz), 7.84 ꢀd, 2H, J9.0Hz), 4.02
ꢀ
1
2
ꢀ
6
4:1) to give a yellow solid ꢀ110mg, 45%), mp 181±
1
13
ꢀm, 4H), 3.75 ꢀm, 4H), 3.18 ꢀm, 4H); C NMR ꢀ75.4 MHz,
828C. H NMR ꢀ300 MHz, CDCl ) d 8.30ꢀd, J15.9 Hz,
3
H), 8.29 ꢀd, J15.9 Hz, 2H), 8.05 ꢀd, J8.7 Hz, 2H), 8.04
CDCl ) d 173.51, 173.42, 134.85, 134.53, 132.84, 132.65,
3
s, 2H), 7.88 ꢀd, J8.7 Hz, 2H), 6.75 ꢀd, J15.9 Hz, 2H),
130.75, 130.40, 129.61, 129.29, 128.06, 124.60, 124.08,
40.92, 25.71, 25.67. MS ꢀEI, 70 eV) m/z ꢀrel. intensity)
498 ꢀ100), 470 ꢀ23), 426 ꢀ36), 351 ꢀ61), 165 ꢀ45). HRMS
1
3
.73 ꢀd, J15.9 Hz, 2H), 3.92 ꢀs, 12H). C NMR
ꢀ
75.4 MHz, CDCl3) d, 166.78, 140.04, 139.97, 136.89,
1
1
1
7
35.32, 135.19, 134.65, 134.60, 131.70, 128.80, 128.75,
28.70, 127.89, 127.40, 127.33, 127.16, 52.34. HRMS ꢀEI,
0eV) calcd for C 36H O ꢀM ) 586.1628, found 586.1638.
ꢀEI, 70eV) calcd for C 32H O ꢀM ) 498.1103, found
18
6
498.1112.
1
26
8
4.1.13. 1,2,5,6-Tetrakisꢀ1-chlorovinyl)corannulene ꢀ24).
4
.1.9. 4,5,10,11-Tetrakisꢀmethoxycarbonyl)acenaphtho-
320mg ꢀ 0. 5 mmol) of 16 was heated to 808C with stirring
in 200 ml of acetic acid and 8 ml of concentrated HCl for
3 h. The reaction mixture was poured onto ice, the dark
precipitate ®ltered, dried ꢀmagnesium sulfate) and chroma-
[
0
3,2,1,8-f,g,h,i, j]picene ꢀ20). A mixture of 19 ꢀ44 mg,
.08 mmol) and DDQ ꢀ45 mg, 0.2 mmol) was re¯uxed
under argon in 15 ml of dry o-xylene for 4 h. The solvent
was evaporated and the solid residue was dissolved in DCM
and ®ltered through a short pad of silica gel. Evaporation of
tographed on silica gel with hot cyclohexane to give 70mg
of yellow solid ꢀ28%). H NMR ꢀ300 MHz, CDCl ) d 8.01
1
3
the solvent gave 24 mg ꢀ55%) of a light brown solid, mp
3
ꢀs, 2H), 7.99 ꢀd, J8.9 Hz, 2H), 7.85 ꢀd, J8.9 Hz, 2H),
1
04±3068C ꢀdec). H NMR ꢀ300 MHz, CDCl ) ꢀconcentra-
13
5.97±6.0ꢀm, 4H), 5.58±5.61 ꢀm, 4H). C NMR
ꢀ75.4 MHz, CDCl ) d 136.58, 135.99, 135.94, 135.10,
3
tion dependent) d, 8.73 ꢀs, 4H), 7.93 ꢀd, J8.7 Hz, 2H), 7.93
3
1
3
ꢀ
ꢀ
s, 2H), 7.68 ꢀd, J8.7 Hz, 2H), 4.08 ꢀs, 12H). C NMR
134.76, 134.47, 131.64, 128.77, 128.64, 128.15, 127.13,
127.05, 120.19, 120.13. HRMS ꢀEI, 70 eV) calcd for
C H Cl ꢀM ) 491.9820, found 491.9827.
75.4 Hz, CDCl ) d 168.24, 168.21, 135.92, 134.38, 134.22,
3
1
1
1
7
34.19, 130.99, 130.15, 130.11, 128.02, 127.62, 127.23,
26.28, 126.20, 124.81, 124.70, 124.56, 53.18. HRMS ꢀEI,
0eV) calcd for C 36H O ꢀM ) 582.1315, found 582.1322.
2
8
14
4
1
FVP of 24. 100 mg of 24 was pyrolyzed at 10258C in a ¯ow
of nitrogen at 1 Torr. The red deposit ꢀca. 5 mg) was
dissolved in DCM, ®ltered through a short pad of silica
22
8
4
.1.10. 4,5,10,11-Tetraphenylacenaphtho[3,2,1,8-f,g,h,i,j]-
1
picene ꢀ21). This procedure was identical to the one
described above for 19 except that methyl acrylate was
gel and analyzed by GC/MS and H NMR indicating a
single product identi®ed as 6.