Bromodimethylsulfonium bromide: A brominating reagent for the conversion of anthracene into 9,10-dibromoanthracene

Article abstract of DOI:10.1016/j.cclet.2013.12.009

Bromodimethylsulfonium bromide (BDMS) was used as an efficient brominating reagent for the synthesis of 9,10-dibromoanthracene in dichloromethane. The desired products were obtained in excellent yields.

Full text of DOI:10.1016/j.cclet.2013.12.009

Chinese Chemical Letters 25 (2014) 435–437
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Chinese Chemical Letters
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Original article
Bromodimethylsulfonium bromide: A brominating reagent for the
conversion of anthracene into 9,10-dibromoanthracene
Xin Zhang, Ju-Yan Liu *, Ying Wang *, Min-Min Yue, Bin Yuan
College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecule, Key Laboratory of Inorganic-Organic Hybrid Functional
Material Chemistry, Ministry of Education, Tianjin Normal University, Tianjin 300387, China
A R T I C L E I N F O
A B S T R A C T
Article history:
Bromodimethylsulfonium bromide (BDMS) was used as an efficient brominating reagent for the
synthesis of 9,10-dibromoanthracene in dichloromethane. The desired products were obtained in
excellent yields.
Received 29 July 2013
Received in revised form 28 October 2013
Accepted 5 November 2013
Available online 8 December 2013
ß 2013 Ju-Yan Liu and Ying Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All
rights reserved.
Keywords:
Bromodimethylsulfonium bromide
Brominating reagent
9
,10-Dibromoanthracene
1
. Introduction
Anthracenes have been extensively investigated in many fields,
reaction medium, and acts as an efficient pre-catalyst for various
acid-catalyzed organic transformations. In continuation of our
recent work on the development of useful new synthetic
methodologies using bromodimethylsulfonium bromide (BDMS)
[22], we have observed that the treatment of anthracene with
bromodimethylsulfonium bromide at room temperature in
dichloromethane afforded the corresponding 9,10-dibromoan-
thracene (Scheme 1).
e.g., material chemistry [1–4], thermochromic or photochromic
fields [5], and organic light-emitting devices [6–12]. Furthermore,
anthracene derivatives have been used in optical, electronic, and
magnetic switches when combined with polymers, films, and
crystals [13,14]. In biological systems, anthracene scaffolds are also
employed for probing DNA cleavage [15]. 9,10-Dibromoanthra-
cene has been used as an important component in fluorescent and
light-emitting polymers [16]. Traditional methods for the prepa-
ration of 9,10-dibromoanthracene involve the bromination of
aromatic hydrocarbons of anthracene via the electrophilic
2. Experimental
2.1. Synthesis of 9,10-dibromoanthracene
substitution of Br
been reported for constructing 9,10-dibromoanthracene in the
presence of ZnBr /NaBiO [18], DBU/Br2/HBr [19], or Br /AcOH
20]. However, molecular bromine has several limitations includ-
ing its volatile, irritating and corrosive nature that makes it a less
than preferable reagent.
Bromodimethylsulfonium bromide (BDMS) can be considered a
convenient storage of molecular bromine, which exhibits both the
properties of a brominating reagent as well as an effective catalyst
2
[17]. Recently, several improved methods have
General procedure for the synthesis of 9,10-dibromoanthra-
cene: A mixture of anthracene (10.0 mmol) and BDMS (24.0 mmol)
in CH Cl (10.0 mL) was stirred for appropriate amount of time at
2
3
2
2
2
[
room temperature [CAUTION!! The reaction produces HBr and a
gas trap (bubbler containing 1 mol/L NaOH solution) should be
used, preferably in a fumehood]. When the reaction completed as
indicated by TLC analysis, the reaction product was collected by
[
21]. It is easier to handle compared to the hazardous molecular
Br
Br
bromine. In addition, BDMS exhibits efficient catalytic properties,
which might be due to its ability to generate in situ dry HBr in the
Br
S
BDMS
CH Cl , r.t.
2
2
*
Corresponding authors.
Br
E-mail addresses: hxxyljy@mail.tjnu.edu.cn (J.-Y. Liu),
wangying790601@163.com (Y. Wang).
Scheme 1. Synthesis of 9,10-dibromoanthracene.
1
001-8417/$ – see front matter ß 2013 Ju-Yan Liu and Ying Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
http://dx.doi.org/10.1016/j.cclet.2013.12.009

4
36
X. Zhang et al. / Chinese Chemical Letters 25 (2014) 435–437
H
H
H
Br
Br
Br
Br
H
H
Me
Me
Me
Me
H
Br
H
Br
H
Br
S
Br
Br
S
Br
Scheme 2. Plausible mechanism for formation of 9,10-dibromoanthracene in the presence of BDMS.
dibromoanthracene formed was found to be of good quality and
purity (mp 222–224 8C, Lit. 226 8C [19,20]). Subsequently, we
applied this unpurified 9,10-dibromoanthracene in lithiation
chemistry with no problems. Also, a plausible mechanism for
the formation of 9,10-dibromoanthracene is shown in Scheme 2.
In the current studies, synthesis of 9,10-dibromoanthracene
requires heating with bromine in carbon tetrachloride giving the
desired compound in 83–88% yield [23], while Graebe and
Liebermann reported a preparation using carbon disulphide as
the reaction solvent [24]. Perhaps the most reliable and commonly
used approach for the preparation of 9,10-dibromoanthracene
involves the reaction of anthracene with bromine in dry dioxane,
giving 9,10-dibromoanthracene in 99% yield [25]. However, in each
of these cases there are problems associated with the use of toxic
molecular bromine.
Fig. 1. The molecular structure of 9,10-dibromoanthracene.
Table 1
Optimization of the reaction condition for the synthesis of 9,10-dibromoanthra-
cene.
4. Conclusion
a
Entry
Solvent
DMSO
Catalyst loading
Time (h)
Yield (%)
In summary, we have developed an improved synthesis of 9,10-
dibromoanthracene that uses mild conditions and inexpensive,
nonvolatile BDMS as a brominating reagent.
1
2
3
4
5
6
7
200 mol%
200 mol%
200 mol%
200 mol%
200 mol%
200 mol%
240 mol%
12
2
12
40
56
30
70
85
96
CH
3
CN
THF
3
1,4-Dioxane
Ethyl acetate
2.5
5
Acknowledgments
CH
CH
2
Cl
Cl
2
2
0.5
0.5
2
This work was supported financially by the Natural Science
Foundation of Tianjin (Nos. 12JCZDJC34300, 11JCYBJC03600),
Young Scientist Fund (No. 21001080).
a
Isolated yield.
filtration. The yellow solid was dried in vacuo for 2 h to give the
1
compound. Mp: 222–224 8C, H NMR (400 MHz, CDCl
4H), 7.66 (4H).
3
):
d
8.60
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[
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[
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