Reductive selenation of aliphatic ketones to dialkyl diselenides with Se-CO-H2O under atmospheric pressure

Full text of DOI:10.1134/S1070428008080228

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 8, pp. 1235–1237. © Pleiades Publishing, Ltd., 2008.
Published in Russian in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 8, pp. 1247–1249.
SHORT
COMMUNICATIONS
Reductive Selenation of Aliphatic Ketones to Dialkyl Diselenides
with Se–CO–H2O under Atmospheric Pressure*
Yahong Chena,b, Fengshou Tianb, Maoping Songb, and Shiwei Luc
a Department of Chemistry, Zhoukou Normal University, Zhoukou, Henan, 466000 China
b Department of Chemistry, Zhengzhou Normal University, Zhoukou, Zhengzhou, Henan, 450052 China
e-mail: fengshoutian@163.com
c Dalian Institute of Chemical Physics, Dalian, Liaoming, 116023 China
Received October 23, 2007
DOI: 10.1134/S1070428008080228
Organoselenium compounds have received consid-
erable attention as useful synthetic reagents and inter-
mediates in organic synthesis. Among them, dialkyl
diselenides are frequently used us starting materials
and reagents in functional group transformations [1].
Many methods have been reported so far for the syn-
thesis of dialkyl selenides. For example, most common
methods involve the reaction of metal diselenides with
alkyl halides [2], dimerization with selenocyanates
[3–5], and oxidation of selenols [6] or selenolates [7].
In addition, dialkyl diselenides can be prepared by the
reaction of carbonyl compounds with hydrogen sele-
nide in the presence of triethylamine in anhydrous
pyridine [8], sodium hydrogen selenide in the presence
of amine and sodium tetrahydridoborate in ethanol [9],
and elemental selenium and sodium tetrahydridoborate
in the presence of amine in EtOH [10] or in the ab-
sence of amine in DMF–EtOH (2:1) [11]. Though all
these methods have their merits they suffer from dis-
advantages such as using strong reducing agents and
highly toxic gas, harsh reaction conditions, and com-
plicated manipulations. Sonoda has also reported that
elemental selenium can be readily reduced with car-
bon(II) oxide and water in the presence of a base to
produce hydrogen selenide which was successfully ap-
plied to the synthesis of dialkyl diselenides from both
aliphatic aldehydes and ketones. However, the process
required fairly high pressure (3.0 MPa), high tempera-
ture (120°C), and long reaction time (24 h) [12].
DMF under atmospheric pressure in the absence of
a base. In this system, aromatic and aliphatic aldehydes
can be reduced and selenated to the corresponding
organic diselenides [13]. Herein we report on a con-
venient synthesis of dialkyl diselenides from aliphatic
ketones with Se–CO–H2O in DMF in moderate to
good yields under atmospheric pressure without a base.
When cyclohexanone (Ia, 2.5 mmol) was reacted
with 1 equiv of selenium (2.5 mmol), carbon(II) oxide
(bubbling), and water (2 ml) in DMF (20 ml) at 90°C
for 7 h, the reductive selenation of Ia efficiently pro-
ceeded to give bis(cyclohexyl) diselenide (Ib) in 74%
yield (Scheme 1). Table shows the results of the reduc-
tive selenation of various ketones with the system Se–
CO–H2O in DMF under atmospheric pressure without
a base. The reaction temperatures varied, depending
on the boiling point of the initial ketone. Reductive
selenation of cyclohexanone and cyclopentanone gave
the corresponding diselenides in good yields (see
table). Under the same conditions, the reactions with
methyl ethyl ketone (IIIa) and diethyl ketone (IVa)
gave the corresponding diselenides IIIb and IVb in
slightly lower yields (48 and 42%, respectively). Ob-
viously, lower steric hindrances in the substrate mole-
cule favor increased yield of the target diselenide.
Scheme 1.
R
R
O
Se, CO, H2O, DMF
–CO2
Se
Se
R'
R
R'
R'
We recently developed a new reduction system in
which hydrogen selenide (H2Se) is formed in situ from
elemental selenium, carbon monoxide, and water in
Ia–VIIIa
Ib–VIIIb
I, RR′ = (CH2)5; II, RR′ = (CH2)4; III, R = Me, R′ = Et;
IV, R = R′ = Et; V, R = Me, R′ = Pr; VI, R = Me, R′ =
C6H13; VII, R = Et, R′ = Bu; VIII, R = Me, R′ = C9H19.
* The text was submitted by the authors in English.
1235

YAHONG CHEN et al.
1236
Scheme 2.
O
O
O
Se, CO, H2O, DMF
–CO2
Me
Me
XIIa
XIIb
Long-chain aliphatic ketones VIa–VIIIa were also
studied, and the corresponding diselenides VIb–VIIIb
were obtained in moderate to good yields. Aromatic
ketones, such as p-chloroacetophenone (IXa), aceto-
phenone (Xa), and 1,3-diphenylpropane-2-one (XIa)
failed to undergo reductive selenation even on pro-
longed heating (10 h); presumably, the reason is steric
hindrance created by the phenyl ring. We also made
an attempt to effect reductive selenation of diketones;
the reaction with 1-phenyl-butane-1,3-dione (XIIa) as
an example led to the formation of the reduction prod-
uct of one carbonyl group, 1-phenylbutan-1-one (XIIb)
with 2.5 mmol of an aliphatic ketone, 2.5 mmol of
selenium, 2 ml of water, 20 ml of DMF, and a mag-
netic stirring bar. Carbon(II) oxide was bubbled
through the mixture under vigorous stirring at 90°C
over a period of 8–10 h. When the reaction was com-
plete, carbon(II) oxide supply was terminated, and the
resulting mixture was stirred for 30 min at room tem-
perature on exposure to air, 20 ml of water was added,
and the mixture was extracted with diethyl ether (3×
40 ml). The combined extracts were dried over anhy-
drous MgSO4, filtered, and evaporated under reduced
pressure to leave a yellow oil which was purified by
column chromatography on silica gel or thin-layer
chromatography to give the pure product. All the prod-
1
[14] (Scheme 2). According to the H NMR data
(CDCl3), the purity of the isolated diselenides was up
to 95%, while unidentified impurities amounted to
about ~5% [15].
1
ucts were identified by H NMR and/or comparison
with authentic samples.
Thus we have developed a convenient method for
the synthesis of dialkyl diselenides from aliphatic
General procedure for the synthesis of organic
diselenides. A 100-ml three-necked flask was charged
Reductive selenation of aliphatic kelones to dialkyl diselenides and NMR spectra of the products
Substrate Product Reaction Yield,a
NMR spectra, δ, δC ppm
1H
13C
no.
no.
time, h
%
Ia
Ib [12]
07
74
3.01–3.05 m (2H), 2.06–2.16 m (4H), 1.25–1.76 m 44.12, 35.30, 27.67, 26.36
(16H)
IIa
IIb [12]
IIIb [11]
IVb [11]
Vb [11]
07
09
09
07
08
08
07
10
60
48
42
64
73
69
61
40
3.50–3.52 m (2H), 2.00–2.02 m (4H), 1.24–1.73 m 43.30, 35.38, 25.61
(8H)
IIIa
IVa
Va
2.99–3.04 m (2H), 1.71–1.77 q (4H), 1.43–1.44 d 42.27, 31.15, 22.84, 13.15
(6H), 0.98–1.01 t (3H)
2.83–2.86 m (2H), 1.75–1.82 q (8H), 0.97–1.00 t 51.27, 30.40, 12.91
(12H)
3.06–3.09 m (2H), 1.69–1.42 m (10H), 0.90–0.94 q 40.80, 30.44, 23.35, 21.89,
(4H), 0.86–0.87 t (6H)
3.03–3.10 m (2H), 1.50–1.71 m (6H), 1.44–1.29 m 40.50, 38.64, 32.49, 29.79,
(20H), 0.87–0.90 t (6H) 28.67, 23.44, 23.35, 14.80
2.89 m (2H), 1.66–1.79 m (8H), 1.26–1.34 m (14H), 49.37, 35.78, 30.67, 29.29,
0.91–1.00 t (6H) 23.26, 14.75, 12.8
3.05–3.11 m (2H), 1.72–1.83 m (6H), 1.70–1.44 m 41.70, 30.82, 26.70, 23.20,
14.83
VIa
VIIa
VIb [15]
VIIb [16]
VIIIa VIIIb [12]
XIIa
XIIb [14]
(12H), 0.90–0.87 t (6H)
14.82, 12.76
7.97–7.95 m (2H), 7.56–7.52 m (1H), 7.53–7.47 m
(2H), 2.96–2.92 t (2H), 1.77–1.72 m (2H), 1.00–
0.97 t (3H)
a
Isolated product.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 8 2008

REDUCTIVE SELENATION OF ALIPHATIC KETONES TO DIALKYL DISELENIDES
1237
6. Krief, A., De Mahieu, A.F., Dumont, W., and Tra-
ketones under atmospheric pressure in the absence of
a base. Further work is now in progress to extend this
methodology to unsymmetrical diselenides.
belsi, M., Synthesis, 1988, p. 131.
7. Krief, A., Van Wemmel, T., Redon, M., Dumont, W.,
and Delmotte, C., Angew. Chem., Int. Ed., 1999, vol. 38,
p. 2245.
8. Margolies, D.S. and Pittman, R.W., J. Chem. Soc.,
1957, p. 799; Cohen, V.I., J. Org. Chem., 1977, vol. 42,
p. 2510.
9. Lewicki, J.W., Günther, W.H.H., and Chu, J.Y.C.,
J. Chem. Soc., Chem. Commun., 1976, p. 552a; Le-
wicki, J.W., Günther, W.H.H., and Chu, J.Y.C., J. Org.
Chem., 1978, vol. 43, p. 2672.
10. Huang, Z.-Z., Liu, F.-Y., Du, J.-X., and Huang, X., Org.
Prep. Proced. Int., 1995, vol. 27, p. 492.
This study was performed under financial support
by the China Postdoctoral Science Foundation (grant
no. 20070410876).
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