Improved method for the synthesis of organic diselenides from organic halides under atmospheric pressure

Article abstract of DOI:10.1080/00397910701465404

An improved approach to the synthesis of organic diselenides is reported. The process involves the reaction of organic halides with selenium, carbon monoxide, and water under atmospheric pressure in the presence of an inorganic base, sodium hydroxide, to afford organic diselenides in good yields. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910701465404

Synthetic Communicationsw, 37: 2687–2692, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701465404
Improved Method for the Synthesis of
Organic Diselenides from Organic Halides
under Atmospheric Pressure
Yahong Chen
Department of Chemistry, Zhoukou Normal University, Zhoukou,
Henan, China
Fengshou Tian
Department of Chemistry, Zhoukou Normal University, Zhoukou,
Henan, China and Department of Chemistry, Zhengzhou University,
Zhengzhou, Henan, China
Maoping Song
Department of Chemistry, Zhengzhou University,
Zhengzhou, Henan, China
Shiwei Lu
Dalian Institute of Chemical Physics, Chinese Academy of Sciences,
Dalian, Liaoning, China
Abstract: An improved approach to the synthesis of organic diselenides is reported.
The process involves the reaction of organic halides with selenium, carbon
monoxide, and water under atmospheric pressure in the presence of an inorganic
base, sodium hydroxide, to afford organic diselenides in good yields.
Keywords: atmospheric pressure, carbon monoxide, organic diselenides, organic
halides, selenium
Received in Japan September 1, 2006
Address correspondence to Fengshou Tian, Department of Chemistry, Zhengzhou
University, Zhengzhou, Henan 450052, China. E-mail: fengshoutian@163.com
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Y. Chen et al.
INTRODUCTION
Organic diselenides have attracted much attention as useful synthetic reagents
and intermediates in organic synthesis.[1] Much effort is being devoted to
accomplishing the preparation of these compounds. The common access to
these compounds is the alkylation of diselenide anions with organic halides.
The diselenide anions have been prepared in many ways: the reduction of
selenium with alkali metals in liquid ammonia[2] or in the presence of an
electron carrier[3] or by ultrasound in THF,[4] sodium hydride,[5] or lithium
aluminum hydride[6] in THF; zinc in the presence of sodium hydroxide in
DMF;[7] samarium diiodide in THF;[8] metal borohydrides[9] and hydrazine[10]
in basic media; or sodium hydroxide under phase-transfer conditions.[11]
Organic diselenides also can be prepared by dimerization with selenocya-
nates[12–14] or oxidation of selenols.[15] Additionally, Sonoda also reported
that elemental selenium can be readily reduced by carbon monoxide
(0.5 Mpa) and water in the presence of an organic base to produce
hydrogen selenide, which was successfully applied to the synthesis of
organic diselenides from alkyl chlorides and acyl chlorides.[16]
RESULTS AND DISCUSSION
In our previous studies on selenium-catalyzed reductive carbonylation of
nitroaromatic compounds with carbon monoxide,[17] we reported the
synthesis of organic diselenides from aromatic and aliphatic aldehydes with
Se/CO/H2O system under atmospheric pressure.[18] On this basis, we
decided to investigate reactions of organic halides with stoichiometric
selenium, carbon monoxide, and water in DMF under atmospheric pressure
in the presence of the inorganic base sodium hydroxide and found that these
reactions led to organic diselenides in good yields:
DMF
2RX þ 2Se þ CO ð1 atmÞ þ H2O þ 2NaOH ꢀꢀꢀ! RSeSeR þ CO2
þ 2NaX þ 2H2O:
When benzyl bromide (1a) was treated with equivalent selenium, carbon
monoxide (bubbling), and water in DMF at 908C for 2 h, the reductive 1a effi-
ciently proceeded to give dibenzyl diselenide (1b) in 75% (entry 1 in Table 1).
The reaction conditions for the synthesis of dibenzyl diselenide (1b) from
benzyl bromide (1a) were also examined in detail and some of the results
are shown in Table 1. From the Table 1 we can see that dimethylformamide
(DMF) is the best solvent for this reaction (entries 1–6 in Table 1); the use
of NaOAc, Et3N, and 1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU) instead of
NaOH as a base led to a decreased yield of 1b (entries 7–9 in Table 1).
We next directed our attention to the preparation of organic diselenides
using this method. The results of synthesis of organic diselenides from

Organic Diselenides from Organic Halides
2689
Table 1. Synthesis of dibenzyl diselenide (1b) from benzyl bromide (1a) under
various conditions
Entrya
Solvent
Temperature (8C)
Base
Yield (%)b
1
2
3
4
5
6
7
8
9
DMF
THF
90
90
75
75
90
90
90
90
90
NaOH
NaOH
NaOH
NaOH
NaOH
NaOH
NaOAc
Et3N
75
43
68
40
70
65
72
70
62
CH3CN
EtOH
DMSO
FPc
DMF
DMF
DMF
DBU
aReaction conditions: benzyl bromide, 2.5 mmol; Se, 2.5 mmol; bubbling CO;
solvent, 20 mL; 2.0 h.
bIsolated yield of 1b.
cFP ¼ 1-formylpiperidine.
various organic halides with the Se/CO/H2O system under atmospheric
pressure are presented Table 2. During the reaction, chlorobenzene, bromo-
benzene, iodobenzene, or benzoyl chloride also did not react at all (entries
1–4 in Table 2). On the contrary, benzyl halides easily reacted and gained
the targeted diselenide products in good yields (entries 5–9 in Table 2). In
the case of alkyl chlorides such as chlorocyclohexane, chlorocyclopentane,
and n-butyl chloride, the desired diselenides were obtained in moderate
yields (entries 10–12 in Table 2). When (1,2-dibromo-ethyl)-benzene was
carried out under similar conditions, side reactions took place to give a
complex mixture.
In conclusion, we have developed an improved method for the synthesis
of organic diselenides from organic halides with a Se/CO/H2O system under
atmospheric pressure in the presence of an inorganic base, sodium hydroxide.
the method described here is a supplement to Sonoda’s method for the prep-
aration of organic diselenides.[16]
EXPERIMENTAL
All melting points were recorded on a WRS-1A melting-point apparatus
1
and were uncorrected. All H 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.

Table 2. Synthesis of organic diselenides from organic halides under various reaction conditions
Entrya
Substrate
Product
Mp (8C)
Yield %b
1
2
3
4
5
PhCl
PhBr
1a
2a
3a
4a
5a
No reaction
No reaction
0
0
PhI
PhCOCl
PhCH2Br
No reaction
No reaction
PhCH2SeSeCH2Ph
0
0
75
5b
6b
7b
8b
87–89
(88–89.5[19]
87–89
)
)
6
7
8
PhCH2Cl
6a
7a
8a
PhCH2SeSeCH2Ph
70
87
73
(88–89.5[19]
96–98
p-BrC6H4CH2Br
o-BrC6H4CH2Br
m-ClC6H4CH2Cl
p-BrC6H4CH2SeSeCH2C6H4Br-p
o-BrC6H4CH2SeSeCH2C6H4Br-o
m-ClC6H4CH2SeSeCH2C6H4Cl-m
(99.5–100.5[11]
96–97
)
(99–100[11]
)
9
10
9a
10a
9b
10b
Yellow liquid[20]
Yellow liquid[21]
76
60
11
12
11a
12a
11b
12b
Yellow liquid[21]
Yellow liquid[16]
64
62
CH3CH2CH2CH2Cl
CH3CH2CH2CH2SeSeCH2CH2CH2CH3
aReaction conditions: organic halide, 2.5 mmol; Se, 2.5 mmol; bubbling CO; H2O, 2 mL; NaOH, 2.5 mmol; DMF, 20 mL; 2.0 h.
bIsolated yield.

Organic Diselenides from Organic Halides
2691
General Procedure for the Synthesis of Organic Diselenides
In a 100-mL, three-necked flask, organic halide (2.5 mmol), selenium
(2.5 mmol), water (2 mL), sodium hydroxide (2.5 mmol), DMF (20 mL),
and a magnetic stirring bar were placed. Carbon monoxide was introduced
and bubbled into the reaction mixture with vigorous stirring at 908C for 2 h.
After the reaction was complete, CO bubbling was stopped, and the
resultant mixture was stirred in air at ambient temperature for 0.5 h.
Water (20 mL) was added, and the reaction mixture was extracted with
diethyl ether (3 ꢁ 40 mL). The organic phase was dried over anhydrous
MgSO4 and filtered, and the solvent evaporated under reduced pressure to
afford a yellow oil or crystal. Further purification by column chromato-
graphy on silica gel or recrystallization gave the pure product. All the
products were identified by NMR and/or comparison with the authentic
samples.
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