Selenium transfer reaction of primary selenoamides: A novel method for the synthesis of diacylselenides from acyl chlorides

Article abstract of DOI:10.1081/SCC-120014047

Diacyl selenides were afford in excent yields by reaction of primary selenoamides with acyl chlorides in chloroform. A possible mechanism is discussed.

Full text of DOI:10.1081/SCC-120014047

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SELENIUM TRANSFER REACTION OF PRIMARY
SELENOAMIDES: A NOVEL METHOD FOR THE SYNTHESIS
OF DIACYLSELENIDES FROM ACYL CHLORIDES
Hua-Rong Zhao a , Xin-Jian Zhao b & Xian Huang a
a Department of Chemistry , Zhejiang University , Hangzhou, 310027, P.R. China
b Zhejiang Institute of Calibaration and Testing for Technical Superision , Hangzhou, 310013,
P.R. China
Published online: 16 Aug 2006.
To cite this article: Hua-Rong Zhao , Xin-Jian Zhao & Xian Huang (2002) SELENIUM TRANSFER REACTION OF PRIMARY
SELENOAMIDES: A NOVEL METHOD FOR THE SYNTHESIS OF DIACYLSELENIDES FROM ACYL CHLORIDES, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:21, 3383-3387, DOI:
10.1081/SCC-120014047
To link to this article: http://dx.doi.org/10.1081/SCC-120014047
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SYNTHETIC COMMUNICATIONS
Vol.32, No.21, pp.3383–3387, 2002
SELENIUM TRANSFER REACTION
OF PRIMARY SELENOAMIDES:
A NOVEL METHOD FOR THE
SYNTHESIS OF DIACYLSELENIDES
FROM ACYL CHLORIDES
Hua-Rong Zhao,1, Xin-Jian Zhao,2 and Xian Huang1
*
1Department of Chemistry, Zhejiang University,
Hangzhou, 310027, P.R. China
2Zhejiang Institute of Calibaration and Testing for
Technical Superision, Hangzhou, 310013, P.R. China
ABSTRACT
Diacyl selenides were afford in excent yields by reaction
of primary selenoamides with acyl chlorides in chloroform.
A possible mechanism is discussed.
Primary selenoamides are rather important intermediates in organic
synthesis.[1] They have been utilized in the preparation of nitrogen- and
selenium-containing heterocyles, such as selenazoles,[2,3] 1,2,4-diselen-
azolines,[4] 1,2,4-selenadiazoles[5,6] and 1,3,5-oxaselenazines.[7] Besides,
selenoamides are also useful for preparation of other selenium-containing
compounds such as selenoesters.[8] However synthetic application of
*Corresponding author.
3383
DOI: 10.1081/SCC-120014047
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3384
ZHAO, ZHAO, AND HUANG
selenoamides has been greatly restricted due to its instability and difficulty in
preparation.We have reported a convenient synthesis of primary seleno-
amides by the reaction of aryl nitriles with sodium hydroselenide in etha-
nol[9] and have also reported that selenobenzamides could react with
reactive halides to afford alkyl diselenides as selenium transfer
reagents.[10–11] We continued investigating the reactivity of primary seleno-
amides toward acyl chloride expecting the reaction would produce acyl
diselenides.When aryl selenoamides were treated with 1 or 2 equimolar
amount of alkyl halides in chloroform at 60ꢀC, in surprise diacyl diselenides
could not be found and diacyl selenides (3a–f ) was formed (Table 1) in
good yields instead (Sch.1).Byproducts aryl nitriles were isolated.
A possible mechanism of above reaction is shown in Sch.2 that
the selenium of selenoamides attacked acyl chlorides twice and formed
the intermediate 6, which then decomposed into diacyl selenides 3 and
nitriles 4.
Diacyl selenides are good acylating agents in organic synthesis.[12]
A
variety of synthetic methods for diacyl selenides have been reported in
literature such as the pyrolysis of selenobenzoic acid,[13] the deselenylation
of diacyl diselenides using triphenylphosphine,[14] the reaction of aliphatic
acyl chlorides with hydrogen selenide,[15] reduction of selenium by carbon
monoxide and following reaction with acyl halides.[16] However, those
Table 1. Preparation of Diacyl Selenides from Selenoamides and Acyl Chlorides
Time
(min)
Isolated Yield
(%)
Entry
R1
C6H5
3-MeC6H4
C6H5
3-MeC6H4
C6H5
C6H5
C6H5
C6H5
R2
C6H5
Product
1
2
3
4
5
6
7
8
3a
3a
3b
3b
3c
3d
3e
3f
60
60
45
40
60
90
120
40
80
82
85
87
81
75
69
80
C6H5
4-MeOC6H4
4-MeOC6H5
4-CH3C6H4
4-ClC6H4
3-ClC6H4
2-Furanyl
Scheme 1.

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SYNTHESIS OF DIACYLSELENIDES
3385
Scheme 2.
methods have the disadvantages of using harmful gases, being in strict
conditions, multiple steps or long reaction time.The present method for
preparation of diacyl selenides has the advantage of easily available starting
materials, simple operation and mild condition compared with them.
EXPERIMENTAL
Melting points were recorded on an electrothermal micro melting
apparatus and are not corrected.IR spectra were recorded on a PE-683
spectrometer, and 1H-NMR spectra were obtained on a JEOL-60S1
spectrometer with TMS as an internal standard.Elemental analyses were
performed on a Carlo Erba 1106 elemental analyzer.
General Procedure for the Reaction
To a solution of selenobenzoamide (1.0 mmol) in chloroform (30 mL)
under N2 atmosphere was added benzoyl chloride (2.5 mmol) slowly at
room temperature.After the completion of addition, the mixture was stirred
at 60ꢀC for 1 h to give a light yellow colour solution.Then the reaction
mixture was washed with water (15 mL), 10% Na2CO3 (15 mL ꢁ 2) and
water (20 mL), dried over anhydrous MgSO4.The solvent was evaporated
and the residue was purified by preparative thin layer chromatography on

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3386
ZHAO, ZHAO, AND HUANG
silica gel (cyclohexane–acetic acid as an eluent), affording pure solid 3a in
80% yield.
3a:[14] M.p. 61–62ꢀC (lit: 61.5–62.3ꢀC).IR: ꢀmax (cmꢂ1) 1736, 1683
1
(C¼O), 1603, 1495. H-NMR: ꢁ 7.30–8.00 (m, 10H).
3b:[14] M.p. 77–78ꢀC (lit: 77.8–80.2ꢀC).IR: ꢀmax (cmꢂ1) 1737, 1688
1
(C¼O), 1608, 1512. H-NMR: ꢁ 3.83 (s, 6H), 6.78–8.04 (m, 8H).
3c:[14] M.p. 89–90.5ꢀC (lit: 90–91ꢀC).IR: ꢀmax (cmꢂ1) 1741, 1692
1
(C¼O), 1610, 1510. H-NMR: ꢁ 2.4 (s, 6H), 7.10–8.00 (m, 8H).
3d:[14] M.p. 117–118ꢀC (lit: 118.5–120ꢀC).IR: ꢀmax (cmꢂ1) 1735, 1687
1
(C¼O), 1599, 1492. H-NMR: ꢁ 7.33–8.03 (m, 8H).
3e:[12] M.p. 91–92ꢀC (lit: 92–93ꢀC).IR: ꢀmax (cmꢂ1) 1735, 1723 (C¼O),
1
1578, 1481. H-NMR: ꢁ 7.40–7.93 (m, 8H).
3f: M.p. 46–47ꢀC.IR: ꢀmax (cmꢂ1) 1737, 1690 (C¼O), 1570, 1465.
1H-NMR: ꢁ 6.55–7.03 (m, 2H), 7.27–7.43 (d, 2H), 7.63–7.77 (d, 2H).
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SYNTHESIS OF DIACYLSELENIDES
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Received in Japan July 17, 2001

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