4H), 1.32 (m, 12H), 0.89 (t, 6H); 13C NMR (75 MHz, CDCl
) δ
80.6, 142.8, 134.9, 131.9, 130.7, 129.6, 127.0, 126.6, 35.9, 31.9,
These procedures were then used to prepare the 2,7-
3
1
3
4
disubstituted pyrenediones 2b, 2c and tetraones 3b, 3c.
1.3, 29.2, 22.8, 14.3; mass calcd for C28
32 2
H O 400.24, found
2
,7-Di(n-hexyl)pyrene-4,5-dione (2c) and 2,7-di-n-hexyl-
00.24 (ESI).
pyrene-4,5,9,10-tetraone (3c) were prepared from the
previously unknown 2,7-di-n-hexylpyrene, which was
synthesized in three steps from 4,5,9,10-tetrahydropy-
rene.
General Procedure for the Preparation of Pyrene-4,5,9,-
1
0-tetraones (3) (Scheme 2). To a solution of the pyrene (1)
(
2 2 3
10 mmol) in CH Cl (40.0 mL) and CH CN (40.0 mL) were
added NaIO (17.5 g, 81.8 mmol), H O (50.0 mL), and RuCl ‚
4
2
3
xH
at 30-40 °C overnight. The reaction mixture was poured into
00 mL of H O, and the solid was removed by filtration. After
the dark green product was washed with 500 mL of H O, the
organic phase was separated. The aqueous phase was extracted
with CH Cl Cl extracts were combined
(3 × 50 mL). The CH
with the organic phase and washed with H
O (3 × 200 mL) to
2
O (0.25 g, 1.2 mmol). The dark brown suspension was heated
Experimental Section
2
2
Pyrene (1a) was purchased from Acros and used as received.
2
2
,7-Di-tert-butylpyrene (1b) was synthesized by using the re-
9
ported procedure in greater than 90% yield. Preparation of 2,7-
di-n-hexylpyrene (1c) is described in the Supporting Information.
General Procedure for the Preparation of Pyrene-4,5-
diones (2) (Scheme 1). To a solution of pyrenes (1) (10 mmol)
2
2
2
2
2
give a dark green solution. The solvent was removed under
reduced pressure to afford a dark green solid that was combined
with the dark green product. Thin-layer chromatography (TLC),
using an ethyl acetate/hexanes (2/5) mixture, indicated the
presence of several byproducts, which were not isolated. Column
in CH
2
Cl
2
(40.0 mL) and CH
O (50.0 mL), and RuCl
.96 mmol). The dark brown suspension was stirred at room
3
CN (40.0 mL) were added NaIO
4
(
0
10.0 g, 46.8 mmol), H
2
3
‚xH O (0.20 g,
2
temperature overnight. The reaction mixture was poured into
chromatography (CH
2 2
Cl ) gave pure products as bright orange
5
00 mL of H
aqueous phase was extracted with CH
Cl extracts were combined with the organic phase and washed
with H
2
O and the organic phase was separated. The
crystals.
2
Cl
2
(3 × 50 mL). The CH
2
-
1
6
3a: yield 36%; mp >350 °C; H NMR (300 MHz, DMSO-d ) δ
8.32 (d, 4H), 7.71 (t, 2H); 13C NMR (N/A, solubility too low); mass
calcd for C H O 262.03, found 262.03 (ESI).
2
2
O (3 × 200 mL) to give an dark orange solution. The
1
6
6
4
solvent was removed under reduced pressure to afford a dark
orange solid. Thin-layer chromatography (TLC), using an ethyl
acetate/hexanes (2/5) mixture, indicated the presence of several
byproducts, which were not isolated. Column chromatography
1
3
3
b: yield 47%; mp 339-342 °C; H NMR (300 MHz, CDCl )
13
δ 8.47(s, 4H), 1.42 (s, 18H); C NMR (75 MHz, CDCl
3
) δ 178.4,
55.1, 134.05 132.4, 130.8, 35.6, 30.9; mass calcd for C24
74.15, found 374.15 (ESI).
c: yield 30%; mp 199-202 °C; H NMR (300 MHz, CDCl
.25 (s, 4H), 2.75 (t, 4H), 1.69 (t, 4H), 1.33 (m, 12H), 0.89 (t,
1
3
22 4
H O
(
CH
a: yield 45%; mp 299-302 °C (lit. mp 302-304 °C); 1H
NMR (300 MHz, CDCl ) δ 8.47 (dd, 2H), 8.16 (dd, 2H), 7.82 (s,
) δ 180.5, 135.9,
2 2
Cl ) gave pure products as bright orange crystals.
1
3
3
) δ
5
a
2
8
6
1
4
3
1
3
3
H); C NMR (75 MHz, CDCl ) δ 178.3, 146.8, 136.8, 132.7,
2
1
2
H), 7.76 (t, 2H); 1 C NMR (75 MHz, CDCl
3
3
30.9, 35.6, 31.7, 30.8, 29.0, 22.7, 14.2; mass calcd for C28
30 4
H O
32.1, 130.2, 130.20, 128.5, 128.1, 127.4; mass calcd for C16
8 2
H O
30.21, found 430.21 (ESI).
32.05, found 232.05 (ESI).
1
2b: yield 46%; mp 241-244 °C; H NMR (300 MHz, CDCl
3
C
)
1
3
Acknowledgment. The support of this work by the
δ 8.54 (dd, 2H), 8.12 (dd, 2H), 7.79 (s, 2H), 1.49 (s, 18H);
NMR (75 MHz, CDCl ) δ 181.2, 51.3, 132.1, 132.0, 130.0, 128.5,
27.5, 126.7, 35.4, 31.4; mass calcd for C24 344.18, found
44.18 (ESI).
c: yield 40%; mp 138-140 °C; H NMR (300 MHz, CDCl
.15 (dd, 2H), 7.78 (dd, 2H), 7.60 (s, 2H), 2.78 (t, 4H), 1.72 (p,
3
Air Force/UA Collaborative Center in Polymer Photonics
is gratefully acknowledged. The Center is funded by the
Air Force Office of Scientific Research, the Air Force
Materials Laboratory, and The University of Akron.
1
3
24 2
H O
1
2
3
) δ
8
Supporting Information Available: Preparation of 2,7-
(
8) (a) Pryor, K. E.; Shipps, G. W., Jr.; Skyler, D. A.; Rebek, J., Jr.
1
13
di-n-hexyl-pyrene (1c) and H and C spectra of all the
compounds were not listed in the text. This material is
available free of charge via the Internet at http://pubs.acs.org.
Tetrahedron 1998, 54, 4107. (b) Stock, L. M.; Wang, S. H. Energy Fuels
1
989, 3, 533. (c) Jeyaraman, R.; Murray, R. W. J. Am. Chem. Soc. 1984,
1
06, 2462.
(
9) Yamato, T.; Fujumoto, M.; Miyazawa, A.; Matsuo, K. J. Chem.
Soc., Perkin Trans. 1 1997, 1201.
JO048509Q
708 J. Org. Chem., Vol. 70, No. 2, 2005