L. W. Jenneskens et al.
FULL PAPER
Acenaphtho[1,2-e]acenaphthylene (4): An enriched fraction contain-
centrated under reduced pressure. The residue was purified by col-
6 3
ing 4 (90%) and 17 (10%) was obtained by preparative column umn chromatography (silica, eluent n-C H14:CHCl , 2:1) giving
chromatography (silica, eluent n-C
of 14. Ϫ H NMR: δ ϭ 8.49 (d, J(H,H) ϭ 7.8 Hz, 1 H), 8.41 (d,
6
H
14) of the 1000°C pyrolysate
0.35 g (0.8 mmol, 80%) of pure 6,12-bis(trimethylsilylethynyl)chry-
sene (22) as a yellow solid. Ϫ M.p. 130Ϫ131°C. Ϫ H NMR: δ ϭ
1
3
1
3
3
J(H,H) ϭ 7.0 Hz, 1 H), 8.19 (s, 1 H), 8.02 (d, J(H,H) ϭ 6.8 Hz, 8.93 (s, 2 H), 8.76 (m, 2 H), 8.50 (m, 2 H), 7.73 (m, 4 H) and 0.40
H), 7.88 (d, J(H,H) ϭ 8.0 Hz, 1 H), 7.86 (d, J(H,H) ϭ 8.2 Hz, (s, 6 H). Ϫ C NMR: δ ϭ 131.5, 129.8, 127.7, 127.4, 127.2, 126.9,
H), 7.75Ϫ7.65 (m, 3 H), 7.62 (d, J(H,H) ϭ 6.9 Hz, 1 H), 7.12 126.4, 123.3, 120.8, 103.6, 100.4 and 0.1. Ϫ GC/MS m/z (%) 420
3
3
13
1
1
3
(100) [M. ]. Compound 22 (0.35 g, 0.8 mmol) was converted into
ϩ
(A part of AB system, J(AB) ϭ 5.2 Hz, 1 H) and 7.08 (B part of
13
AB system, J(AB) ϭ 5.2 Hz, 1 H) ppm. Ϫ C NMR: δ 129.6, 15 by treatment with anhydrous K
29.5, 128.4, 128.2, 128.0, 127.4, 127.3, 124.6, 124.1, 123.8, 121.0 mL) at room temperature for 3 hours. After removal of the solvent
and 118.7 (ten quaternary C atoms not resolved). Ϫ GC/MS m/z under reduced pressure CHCl (50 mL) was added and the re-
2 3 3
CO (0.06 g) in CH OH (30
1
3
.
ϩ
(
%) 276 (100) [M ]. Ϫ HRMS (C22
H
12) Calcd. 276.0939; found sulting solution washed with water (2 ϫ 20 mL). The organic layer
276.0910.
was dried over magnesium sulfate and concentrated under reduced
pressure. Pure 15 was obtained as an off white solid (0.14 g, 0.5
Cyclopenta[cd]perylene (5): Pure 5 was isolated from the 1000°C
pyrolysate of 23. The pyrolysate was collected with CH Cl (10 mL)
followed by removal of the solvent in vacuo. Addition of C OH
0.02 g mL ) gave a deeply red coloured solution from which 5
mmol, 61%). Even upon storage at Ϫ20°C 15 slowly oligo cq. poly-
merizes. Ϫ DSC; m.p. endotherm not discernible, i.e. in the first
heating run only one exotherm (175Ϫ230°C with ∆H Ϫ31.8 kcal
2
2
2 5
H
Ϫ1
(
Ϫ1
1
mol , see text and Figure 3) was found. Ϫ H NMR: δ ϭ 8.99 (s,
crystallized at 4°C. Yield 51%, red crystals, m.p. > 300°C (dec.). -
2
Ϫ
H), 8.77 (m, 2 H), 8.54 (m, 2 H), 7.75 (m, 4 H) and 3.60 (s, 2 H).
1
3
3
H NMR: δ ϭ 8.46 (d, J(H,H) ϭ 7.5 Hz, 2 H), 8.28 (d, J(H,H) ϭ
1
3
C NMR: δ ϭ 131.6, 129.8, 127.7, 127.6, 127.3, 127.0, 126.9,
3
3
7
7
7
1
.5 Hz, 2 H), 7.85 (d, J(H,H) ϭ 7.6 Hz, 2 H), 7.81 (d, J(H,H) ϭ
.
ϩ
1
23.2, 120.1, 82.6 and 82.2. Ϫ GC/MS m/z (%) 276 (100) [M ]. Ϫ
12 (276.34): calcd. C 95.62, H 4.38; found C 95.42, H 4.32.
3
.5 Hz, 2 H), 7.61 (dd, J(H,H) ϭ 7.5 Hz and 7.6 Hz, 2 H) and
22
C H
.13 (s, 2 H). Ϫ 13C NMR: δ ϭ 138.0, 131.7, 129.8, 129.7, 128.9,
28.3, 126.5, 125.2, 122.5 and 120.0 (three quaternary C atoms not
9-Ethynylbenz[j]acephenanthrylene (16): Selected spectral data for
.ϩ
resolved). Ϫ GC/MS m/z (%) 276 (100) [M ]. Ϫ C22
H
12 (276.34): 16 were derived from the 900°C pyrolysate of 14 by comparison
1
calcd. C 95.62, H 4.38; found C 95.39, H, 4.34.
with available spectroscopic data of 4, 15 and 17 (Table 3). Ϫ H
4
NMR: δ ϭ 8.95 (s, 1 H), 8.94 (s, 1 H), 8.84 (dd, J(H,H) ϭ 1.7
Cyclopenta[def]benzo[hi]chrysene (6): A small amount of analyti-
cally pure 6 (ca. 5 mg) was obtained by tedious preparative HPLC
3
4
Hz, J(H,H) ϭ 7.2 Hz, 1 H), 8.60 (m, 1 H), 8.45 (dd, J(H,H) ϭ
1
3
.7 Hz, J(H,H) ϭ 7.2 Hz, 1 H), 7.75 (m, 4 H), 7.24 (AB system,
1
of the 1200°C pyrolysate of 3. Ϫ H NMR ([D
6
]acetone): δ ϭ 8.59
J(AB) ϭ 5.3 Hz, 1 H), 7.22 (AB system, J(AB) ϭ 5.3 Hz, 1 H) and
4
(
dd, 3J(H,H) ϭ 7.2 Hz, J(H,H) ϭ 1.0 Hz, 1 H), 8.53 (dd,
J(H,H) ϭ 8.3 Hz, J(H,H) ϭ 1.0 Hz, 1 H), 8.42 (d, J(H,H) ϭ
ϩ
3
.59 (s, 1 H). Ϫ GC/MS m/z (%) 276 (100) [M. ].
3
4
3
3
3
8
.6 Hz, 1 H), 8.13 (d, J(H,H) ϭ 8.6 Hz, 1 H), 8.07 (dd, J(H,H) ϭ Bis(cyclopenta[hi,qr])chrysene (17): Pure 17 was isolated from the
8
.3 Hz, 4J(H,H) ϭ 1.0 Hz, 1 H), 8.06 (dd, J(H,H) ϭ 8.3 Hz,
3
900Ϫ1000°C pyrolysate of 14 by recrystallization from toluene (10
4
3
Ϫ1
J(H,H) ϭ 1.0 Hz, 1 H), 7.92 (d, J(H,H) ϭ 8.1 Hz, 1 H), 7.91 (d, mg mL ). Isolation of 17 from the T > 1000°C pyrolysates is
3
3
3
J(H,H) ϭ 6.9 Hz, 1 H), 7.78 (dd, J(H,H) ϭ 8.3 Hz, J(H,H) ϭ thwarted due to co-precipitation of 4 and 17. Yield 31%, orange
3
3
1
7
7
(
.2 Hz, 1 H), 7.75 (dd, J(H,H) ϭ 8.3 Hz, J(H,H) ϭ 8.4 Hz, 1 H), crystals, m.p. 235°C (dec.). Ϫ H NMR: δ ϭ 8.94 (s, 2 H), 8.55
3
3
4
3
.70 (dd, J(H,H) ϭ 8.1 Hz and J(H,H) ϭ 6.9 Hz, 1 H) and 7.61 (dd, J(H,H) ϭ 1.7 Hz, J(H,H) ϭ 7.2 Hz, 2 H), 7.74 (m, 4 H),
]acetone): δ ϭ 131.6, 130.7, 129.8, 129.6, 7.25 (AB system, J(AB) ϭ 5.3 Hz, 2 H) and 7.22 (AB system,
27.8, 127.3, 126.0, 125.4, 125.2, 125.1, 120.0 and 119.9 (ten quater-
s, 1 H). Ϫ 13C NMR ([D
6
1
3
1
J(AB) ϭ 5.3 Hz, 2 H). Ϫ C NMR: δ ϭ 139.8, 139.1, 131.9, 131.2,
nary C atoms not resolved) (see IGLOIII//6Ϫ31G Calculations). Ϫ
129.0, 128.2, 127.1, 126.8, 123.2, 122.6 and 120.6. Ϫ GC/MS m/z
(%) 276 (100) [M ]. Ϫ C22H12 (276.34): calcd. C 95.62, H 4.38;
GC/MS m/z (%) 276 (100) [M. ]. Ϫ HRMS (C22
ϩ
H12): calcd.
.ϩ
276.0939; found 276.0906.
found: C 95.36; H 4.46.
6,12-Bis(1-chloroethenyl)chrysene (14): Compound 15 (0.48 g, 1.1
6,12-Dibromochrysene (21): Chrysene (1.00 g, 4.4 mmol) was
mmol) was converted into 14 by treatment with HCl gas in acetic treated with 15.0 g (22.4 mmol) of alumina-supported copper (II)
bromide[ in CCl
21]
(50 mL) at reflux temperature for four days.
acid (50 mL) at 80°C for 1 h. Subsequently, water (100 mL) was
added and the resulting mixture extracted with CHCl (3 ϫ 50 After filtration the residue was washed with 200 mL hot CCl
mL). The organic layer was washed with a saturated solution of combined filtrate was concentrated under reduced pressure and the
NaHCO in water, dried over magnesium sulfate and concentrated remaining solid was recrystallized from CHCl giving pure 21 (1.25
4
3
4
. The
3
3
1
under reduced pressure. Pure 14 was obtained as yellow solid (0.40
g, 3.2 mmol, 74%) as white crystals. Ϫ M.p. 260°C (dec.). Ϫ H
1
g, 1.1 mmol, 100%). Ϫ M.p. 188°C (dec.). Ϫ H NMR: δ ϭ 8.80
NMR: δ ϭ 9.00 (s, 2 H), 8.70 (m, 2 H), 8.44 (m, 2 H) and 7.78 (m,
4
3
13
(
(
5
dd, J(H,H) ϭ 1.4 Hz, J(H,H) ϭ 9.1 Hz, 2 H), 8.73 (s, 2 H), 8.33 4 H). Ϫ C NMR: δ ϭ 130.8, 130.5, 128.2, 128.1, 127.9, 127.8,
4
3
dd, J(H,H) ϭ 1.7 Hz, J(H,H) ϭ 7.7 Hz, 2 H), 7.74 (m, 4 H),
125.2, 123.3 and 123.2. Ϫ C22
.97 (d, J(H,H) ϭ 0.8 Hz, 2 H) and 5.75 (d, J(H,H) ϭ 0.8 Hz, 2 2.61; found C 55.76, H, 2.60.
2
H10Br (434.13): calcd. C 56.00, H
2
2
13
H). Ϫ C NMR: δ ϭ 139.0, 126.7, 130.8, 129.3, 127.9, 127.2,
3
-(1-Chloroethenyl)perylene (23): A mixture of 24 (0.71 g, 2.4
mmol) and PCl (0.70 g, 3.6 mmol) in PCl (50 mL) was heated at
0°C for 3 h. After cooling to room temperature water (100 mL)
was added. After standard workup, and purification by preparative
/n-C 12, 1:1) 23 was
mmol) was added to a deaereated solution of 0.40 g (1.04 mmol) isolated as a yellow solid. Yield 0.68 g (2.2 mmol, 93%). Ϫ M.p.
1
3
27.0, 126.3, 123.4, 122.0 and 118.2. Ϫ GC/MS m/z (%) 348 (100),
50 (67), 352 (12) [M with appropriate isotope pattern].
.
ϩ
5
3
4
6,12-Bis(ethynyl)chrysene (15): Bis(triphenylphosphane)palladium
dichloride (0.28 g, 0.4 mmol), and copper(I) iodide (0.02 g, 0.1 column chromatography (silica, eluent CHCl
3
5
H
1
3
of 6,12-dibromochrysene (20) and 0.30 g (3.1 mmol) of ethynyltri-
140°C (dec.). Ϫ H NMR: δ ϭ 8.22 (m, 3 H), 8.14 (d, J(H,H) ϭ
methylsilane in anhydrous triethylamine (40 mL).[ The reaction 7.8 Hz, 1 H), 8.03 (d, J(H,H) ϭ 8.4 Hz, 1 H), 7.71 (d, J(H,H) ϭ
22]
3
3
3
mixture was heated at reflux temperature for 5 days. After cooling 8.1 Hz, 1 H), 7.70 (d, J(H,H) ϭ 8.0 Hz, 1 H), 7.53 (m, 4 H), 5.85
2
2
to room temperature the solid was filtered off and the filtrate con-
(d, J(H,H) ϭ 1.1 Hz, 1 H) and 5.61 (d, J(H,H) ϭ 1.1 Hz, 1 H).
1198
Eur. J. Org. Chem. 1999, 1191Ϫ1200