sensors in biological and supramolecular systems,4 organic
gellators,5 etc. For example, 9,10-di-2-naphthylanthracene3f and
9,10-di(triisopropylsilyl)ethynylanthracene3g have been used
successfully as blue emitters with efficient electroluminescene.
Furthermore, anthracenes possess efficient photochromic prop-
erties that can find a variety of applications in data storage or
molecular switches.6 Substituted anthracenes have been prepared
by Friedel-Crafts reaction,7 aromatic cyclodehydration,8 E1bs
reaction,9 Lewis acid-induced Bradsher-type reaction from
diarylmethanes,10 homologation mediated by metallacycles,11
and so on. Nevertheless, enhancing the efficiency of the
synthesis of these compounds that allow selective formation of
anthracenes from readily available precursors is still highly
attractive. In 1966, Miller reported that various substituted
anthracenes could be obtained by acids-promoted transannular
cyclodehydration of 1,2-bis(R-hydroxy-substituted-benzyl)ben-
zenes (prepared by reduction of 1,2-diaroylbenzene).12 However,
the reaction generally required high reaction temperatures and
large amounts of strong Brønsted acids, and it was noncatalytic.
The preparation of starting 1,2-diaroylaromatics also presented
difficulty. It was demonstrated that in the reaction, the undesired
phthalan formation still remained a problem.12,13 On the basis
of our recent work,14 we found that anthracenes could be
constructed selectively by a TfOH-catalyzed cyclization reaction.
Herein, we described a highly efficient and a mild, one-pot
procedure by a Brønsted acid-catalyzed intramolecular Friedel-
Crafts reaction/aromatization to substituted arylanthracenes and
heteroacenes (Scheme 1). The yield of this process ranged from
56% to 99% and the side product of the phthalan derivative
was below 10% in most cases.
Improved Synthesis of Aryl-Substituted
Anthracenes and Heteroacenes
Guijie Li,† Shaolin Zhou,† Guowei Su,†
Yuanhong Liu,*,† and Peng George Wang‡
State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, 354 Fenglin Lu, Shanghai 200032, People’s Republic
of China, and Department of Chemistry and Biochemistry,
The Ohio State UniVersity, Columbus, Ohio 43210
ReceiVed August 9, 2007
A Brønsted acid-catalyzed highly efficient construction of
substituted arylanthracenes and heteroacenes is described,
which is assumed to be initiated through the facile formation
of a benzylic cation intermediate. This method offers several
advantages in comparison with known aromatic cyclodehy-
dration reactions such as high selectivities, mild reaction
conditions, and easily accessible starting materials.
The requisite substrates of aromatic diols and its ester
derivatives could be easily prepared in generally good to high
yields as a diastereomeric mixture through Grignard addition
to phthalaldehyde.15 In view of the highly catalytic activity in
our work on TfOH-catalyzed reactions,14 we first examined the
Anthracene and its derivatives are one of the most important
classes of polycyclic aromatic compounds.1 Due to their unique
electronic and photonic properties, they have been proved
extremely versatile in material science such as in organic field
effect transistors (OTFT),2 organic light-emitting diodes (OLED),3
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† Shanghai Institute of Organic Chemistry.
‡ The Ohio State University.
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(13) We did not find the related work after this study.
(14) Zhou, S.; Li, G.; Liu, Y.; Wang, P. Submitted for publication.
(15) See the Supporting Information.
10.1021/jo7017334 CCC: $37.00 © 2007 American Chemical Society
Published on Web 11/10/2007
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J. Org. Chem. 2007, 72, 9830-9833