1136
J . Org. Chem. 1996, 61, 1136-1139
new two-step procedure for the addition of an aromatic
Gr a m Sca le Syn th esis of
Ben zo[gh i]p er ylen e a n d Cor on en e†
six-membered ring to an existing aromatic hydrocarbon.
This is performed via addition and closure of a two-carbon
chain over a bay region. This procedure has resulted in
the very facile and high-yield, two-step synthesis of
benzo[ghi]perylene (4) from perylene (2). Using the same
procedure, 4 can be transformed into coronene (6) very
efficiently. This reaction can easily be performed on a
gram scale.
J oost T. M. van Dijk, Astrid Hartwijk,
Annemarie C. Bleeker, J ohan Lugtenburg, and
J an Cornelisse*
Leiden Institute of Chemistry, Gorlaeus Laboratories, P.O.
Box 9502, 2300 RA Leiden, The Netherlands
Received August 23, 1995
Resu lts a n d Discu ssion
In tr od u ction
Because perylene (2) is not available in large quanti-
ties, we first optimized its synthesis. In most of the
reported syntheses, 3,4,9,10-perylenetetracarboxylic di-
anhydride (1) is converted into perylene. Early workers
have reported the synthesis of perylene from 1 in varying
yields using intricate procedures such as passing super-
heated steam or conversion at high pressure.15,16 We
have now simplified and optimized the synthesis of
perylene from 1. This was achieved by simply mixing
finely powdered barium hydroxide and 1 in a 4:1 ratio
and heating this mixture in a Pyrex tube in a furnace at
80 °C for 2 h. Perylene could subsequently be harvested
by sublimating it to the parts of the tube outside the oven
at 380 °C, a process which lasts about 5 days. Using this
very mild procedure, perylene is obtained in high purity
in yields of up to 80% (Scheme 1).
Polycyclic aromatic hydrocarbons (PAH) are formed
during various kinds of combustion processes1 and thus
find their way into the environment.2 This poses a threat
for public health because of the toxic effect of some of
the PAH.3 Furthermore, PAH are used as organic
conductors,4 in solar cell research,5 in polymer research,6
and in many other fields of research.
Because most of the classical syntheses of PAH involve
rather vigorous conditions such as pyrolysis of aromatic
precursors,7 in recent years milder methods giving higher
yields and higher selectivities have been explored.8 This
usually resulted in multistep syntheses consisting of the
addition of two-, three-, or four-carbon chains to the arene
followed by cyclization and dehydrogenation. In this way
the desired aromatic five- or six-membered rings may be
formed. An example of ring formation in one step is the
Diels-Alder reaction, in which the arene usually acts as
the dienophile.9 The only example known of the forma-
tion of a six-membered ring by the addition of a two-
carbon unit is the Diels-Alder reaction of PAH contain-
ing a bay region with maleic anhydride or other electron-
poor alkenes.10,11 This usually gives low to moderate
yields as does the subsequent decarboxylation.
Usually, the conversion of PAH into their anions with
alkali metals is conducted in liquid ammonia,17 which
catalyzes the transfer of electrons. We have developed
a new and facile way of generating the perylene dianion
on a gram scale from neutral perylene and alkali metals.
By ultrasonic vibration for 3 h of a suspension of perylene
and sodium in dry degassed THF, we obtained a deep
purple solution of 22- in very high conversion (Scheme
2). When the same procedure was followed using THF-
d8 as a solvent in an NMR tube, again a deep purple
In our group we focus on the synthesis of PAH via the
use of anions of PAH, derived either via deprotonation
or via reduction with alkali metals, because of the high
selectivity of these anions. This has resulted in the
synthesis of cyclopenta[cd]pyrene,12 benzo[e]pyrene,13 and
other new PAH.14 We now report the development of a
1
solution was obtained with a H NMR spectrum identical
to that published for the perylene dianion (22-).18 The
advantage of this method is that due to the absence of
liquid ammonia, a larger scope of different reaction
conditions can be applied to the anion and a greater
number of electrophiles may be allowed to react with the
anion.
† Dedicated to Professor Hans-Dieter Scharf on the occasion of his
65th birthday.
(1) Bjørseth, A.; Ramdahl, T. Handbook of Polycyclic Aromatic
Hydrocarbons; Bjørseth, A., Ramdahl, T., Eds.; Marcel Dekker, Inc.:
New York, 1985; Vol. 2, Chapter 1.
(2) Shabad, L. M. J . Natl. Cancer Inst. 1980, 64, 405.
(3) Li, K.-M.; Todorovic, R.; Rogan, E. G.; Cavalieri, E. L.; Ariese,
F.; Suh, M.; J ankowiak, R.; Small, G. J . Biochemistry 1995, 34, 8043.
(4) Gama, V.; Henriques, R. T.; Bonfait, G.; Almeida, M.; Meetsma,
A.; van Smaalen, S.; de Boer, J . L. J . Am. Chem. Soc. 1992, 114, 1986.
Dias, C. B.; Santos, I. C.; Gama, V.; Henriques, R. I.; Almeida, M.;
Pouget, J . P. Synth. Met. 1993, 56, 1688.
(5) Hiramoto, M.; Kishigami, Y.; Yokoyama, M. Chem. Lett. 1990,
119.
(6) Tyutyulkov, N.; Karabunarliev, S.; Mu¨llen, K.; Baumgarten, M.
Synth. Met. 1993, 53, 205. Anton, U.; Mu¨llen, K. Makromol. Chem.,
Rapid Commun. 1993, 14, 223.
When reduction is complete, the solution of the dianion
can be brought to any desired temperature, after which
it can be allowed to react with an electrophile. We found
that reaction of 22- with bromoacetaldehyde diethyl
acetal at -65 °C and subsequent addition of iodine
results in the formation of 1-peryleneacetaldehyde diethyl
acetal (3) in 83% yield (Scheme 3), together with 10% of
perylene and 5% of the 3-alkylated isomer. Perylene can
be removed from 3 and 3-peryleneacetaldehyde diethyl
acetal by means of column chromatography using toluene
as the eluent. Via this method we can easily synthesize
a 1-substituted perylene, contrary to Friedel-Crafts and
related reactions, from which 3-substituted perylenes are
obtained.8
(7) Fieser, L. F. Org. React. (N. Y.) 1942, 1, 129-54.
(8) Harvey, R. G. Polycyclic Aromatic Hydrocarbons; Cambridge
Monographs on Cancer Research; Cambridge University Press: Cam-
bridge, 1991.
(9) Kloetzel, M. C.; Mertel, H. E. J . Am. Chem. Soc, 1950, 72, 4786.
(10) Clar, E.; Zander, M. J . Chem. Soc. 1957, 4616.
(11) Ott, R.; Wiedemann, F.; Zinke, A. Monatsh. Chem. 1968, 99,
2032.
(12) Tintel, C.; Cornelisse, J ; Lugtenburg, J . Recl. Trav. Chim. Pays-
Bas 1983, 102, 14.
(13) Tintel, C.; Lugtenburg, J .; van Amsterdam, G. A. J .; Erkelens,
C.; Cornelisse, J . Recl. Trav. Chim. Pays-Bas 1983, 102, 228.
(14) van Dijk, J . T. M.; Lugtenburg, J .; Cornelisse, J . J . Chem. Soc.,
Perkin Trans. 2 1995, 1489.
Addition of sulfuric acid to a heterogeneous mixture
of methanol, 3, and 3-peryleneacetaldehyde diethyl acetal
(15) Gotoh, N. Yuki Gosei Kagaku Kyokaishi 1970, 28, 1178.
Iwashima, S.; Aoki, J . Bull. Chem. Soc. J pn. 1968, 41, 2789.
(16) Rogovik, V. I.; Solomentseva, T. I. J . Org. Chem. USSR (Engl.
Transl.) 1985, 21, 2045.
(17) Rabideau, P. W.; Marcinow, Z. Org. React. (N. Y.) 1992, 42, 1.
(18) Ebert, L. B. Tetrahedron 1986, 42, 497.
0022-3263/96/1961-1136$12.00/0 © 1996 American Chemical Society