An improved synthesis of symmetrical diselenides from aromatic aldehydes

Article abstract of DOI:10.1080/10426500902967912

An improved method for the synthesis of symmetrical diselenides is described. Reductive selenation of aromatic aldehydes with Se/CO/H2O/Et3N system in THF gave the corresponding aromatic diselenides in good yields.

Full text of DOI:10.1080/10426500902967912

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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An Improved Synthesis of Symmetrical
Diselenides from Aromatic Aldehydes
Yahong Chen a , Fengshou Tian a b , Maoping Song b & Shiwei Lu c
a Department of Chemistry , Zhoukou Normal University , Zhoukou,
Henan, P. R. China
b Department of Chemistry , Zhengzhou University , Zhengzhou,
Henan, P. R. China
c Dalian Institute of Chemical Physics , Dalian, Liaoning, P. R. China
Published online: 23 Mar 2010.
To cite this article: Yahong Chen , Fengshou Tian , Maoping Song & Shiwei Lu (2010) An Improved
Synthesis of Symmetrical Diselenides from Aromatic Aldehydes, Phosphorus, Sulfur, and Silicon and
the Related Elements, 185:4, 799-802, DOI: 10.1080/10426500902967912
To link to this article: http://dx.doi.org/10.1080/10426500902967912
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Phosphorus, Sulfur, and Silicon, 185:799–802, 2010
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500902967912
AN IMPROVED SYNTHESIS OF SYMMETRICAL
DISELENIDES FROM AROMATIC ALDEHYDES
Yahong Chen,1 Fengshou Tian,1,2 Maoping Song,2
and Shiwei Lu3
1Department of Chemistry, Zhoukou Normal University, Zhoukou, Henan,
P. R. China
2Department of Chemistry, Zhengzhou University, Zhengzhou, Henan, P. R. China
3Dalian Institute of Chemical Physics, Dalian, Liaoning, P. R. China
An improved method for the synthesis of symmetrical diselenides is described. Reductive sele-
nation of aromatic aldehydes with Se/CO/H2O/Et3N system in THF gave the corresponding
aromatic diselenides in good yields.
Keywords Aromatic aldehydes; carbon monoxide; diselenides; selenium
INTRODUCTION
Organoselenium compounds are very important organic synthetic reagents and in-
termediates.1 Among them, symmetrical diselenides are versatile reagents and potential
medicinal agents.2 Several methods have been reported for the synthesis of symmetrical
diselenides.3 For example, Nishiyama et al. found that aliphatic aldehydes and ketones can
reduce selenation to aliphatic diselenides using a Se/CO/H2O/base.4
RESULTS AND DISCUSSION
In the course of our studies on selenium-catalyzed reductive carbonylation of ni-
troaromatic compounds with carbon monoxide, we developed a new application of the
Se/CO/H2O system to convert aromatic aldehydes,5 organic halides,6 or imines7 to sym-
metrical diselenides. However, the disadvantages of these methods are long reaction times
(7–9 h) and undesirable byproducts (symmetrical urea). We report in this article an efficient
method for synthesizing symmetrical diselenides (yields up to 89%) by reactions of sele-
nium and aromatic and heterocyclic aldehydes in the presence of carbon monoxide, water,
and triethylamine (Scheme 1).
Treatment of benzaldehyde (1a) with one equivalent selenium in THF at 100◦C in
the presence of carbon monoxide (3 Mpa), water, and Et3N for 3 h led to efficient reductive
Received 26 September 2008; accepted 14 April 2009.
We acknowledge the financial support from China Postdoctoral Science Foundation (No. 20070410876).
Address correspondence to Fengshou Tian, Department of Chemistry, Zhoukou Normal University, Zhoukou,
Henan 466000, P. R. China. E-mail: fengshoutian@163.com
799

800
Y. CHEN ET AL.
THF
Se
+
+ H 2O
+
CO
A rCH O
1
ArCH 2S eS eCH 2A r
2
Et3 N
a) Ar = C6H5; b) Ar = p-MeC6H4; c) Ar = m-MeC6H4; d) Ar = o-MeC6H4; e) Ar = p-
MeOC6H4; f) Ar = o- MeOC6H4; g) Ar = m- C6H4OH; h) Ar = 2-thienyl; i) Ar = 3-
thienyl; j) Ar = 3-pyridyl
Scheme 1
selenation to give dibenzyl diselenide (1b) in 85% yield (Table I, entry 1). No byproduct
such as benzyl alcohol or toluene was detected from the reaction mixture. Although the pho-
tochemical reaction of ketones and aldehydes with hydrogen selenide afforded alcohols,8
acetophenone did not undergo selenation, and only a trace amount of ethylbenzene was
detected in the reaction mixture (GC-MS analysis).9 The reaction did not proceed without
water or without use of base. The results with other aromatic and heterocyclic aromatic
aldehydes are summarized in Table I. Increasing steric hindrance on the aromatic ring led to
decreased yields, but steric effects of the substituents only slightly affect yields of the dise-
lenides (Table I, entries 1–6). Salicylaldehyde was unchanged under the reaction conditions
(Table I, entry 7). Heterocyclic-aromatic aldehydes (2-and 3-thiophenecarboxaldehydes,
Table I Synthesis of symmetrical diselenides from aromatic aldehydesa
Entry Diselenide Yield (%)
Mp (◦C) (lit.)
92–93 (90–91)10
59–60 (61–62)11
Yellow liquid5
1H NMR (δ)
13C NMR (δ)
1
2
3
2a
2b
2c
85b
89
7.37–7.26 (m, 10H),
3.88 (s, 4H)
7.26–7.10 (s, 8H), 3.84 149.70, 129.84, 126.56,
(s, 4H), 2.32 (s, 6H) 112.44, 40.60, 32.90
7.36–7.22 (m,8H), 3.98 138.62, 137.54, 129.5,
139.05, 129.04, 128.45,
127.21, 32.66
82
(s, 4 H), 2.52 (s, 6 H)
128.05, 127.56, 125.82,
32.38, 21.19
152.32, 142.85, 111.03,
108.88, 107.70, 24.86,
18.91
4
2d
78
80–81 (86–86.5)3c 7.42–6.22 (m, 8H),
3.96 (s, 4H), 3.81 (s,
6H)
7.26–6.83 (m,8H), 3.83 138.99, 128.21, 125.82,
(s,4H), 3.80 (s,6H) 122.52, 26.36
7.26–6.84 (m,4H), 3.98 149.84, 148.36, 136.22,
5
6
2e
2f
86
81
72–73 (72)12
66–67 (–)13
(s, 4H), 3.87 (s, 6H)
134.52, 123.32, 28.72,
24.53
7
8
2g
2h
—
82
—
Yellow liquid5
7.43–6.23 (m, 6H),
3.96 (s, 4 H)
7.27–7.02 (m, 6H),
3.86 (s, 4 H)
8.46–7.18 (m, 8H),
3.72 (s, 4H)
152.23, 142.64, 111.35,
108.54, 24.52
138.99, 128.28, 125.80,
122.52, 26.36
149.84, 148.39, 136.22,
123.32, 28.72
9
2i
2j
85
88
94–965 (94–96)5
77–795 (77–79)5
10
aAll experimental reaction.
bYield is only 32% in toluene.

SYNTHESIS OF SYMMETRICAL DISELENIDES
801
and 3-pyridinecarboxaldehyde) were also efficiently transformed to their corresponding
diselenides in good yields (82%–88%) (Table I, entries 8–10).
EXPERIMENTAL
All melting points were recorded on a WRS-1A melting-point apparatus and are un-
corrected. All 1H NMR spectra were recorded on a 400-MHz Bruker AZ 400 spectrometer.
Chemical shifts are given as d value with reference to tetramethylsilane (TMS) as internal
standard. Carbon monoxide (99.9%) was dried by zeolite 5A. Elemental selenium (99.5%)
and the reagents were received from commercial supply without purification prior to use.
PROCEDURE FOR SYNTHESIS OF AROMATIC DISELENIDES
The aromatic aldehyde (2.5 mmol), selenium (2.5 mmol), water (25 mmol), Et3N
(2.5 mmoL), and THF (10 mL) and a magnetic stirring bar were successively loaded into a
70-mL stainless-steel autoclave. The reactor was sealed, flushed three times with 1.0 MPa
of carbon monoxide, pressurized with 3.0 MPa of carbon monoxide, and then placed in
an oil bath preheated to 100◦C. After the reaction was complete, the apparatus was cooled
to ambient temperature, and the remaining carbon monoxide was evacuated. Then water
(20 mL) was added, and the reaction mixture was extracted with diethyl ether (3 × 40 mL).
The combined organic extracts were dried over anhydrous MgSO4, filtered, and the solvent
was evaporated under reduced pressure to afford a yellow oil. Further purification by column
chromatography on silica gel or TLC gave the pure product. All the products were identified
by NMR and/or comparison with authentic samples.
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