A novel synthesis of selenides and selenol esters using liquid-liquid phase-transfer catalysis

Article abstract of DOI:10.1080/10426500307940

This article describes the first attempt to synthesize selenides and selenol esters prepared from the reaction of 1-benzyl or 1-acyl-selenophenylmethaniminium halides and organic halides under liquid-liquid phase-transfer conditions. This method also can

Full text of DOI:10.1080/10426500307940

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Phosphorus, Sulfur, and Silicon and the Related
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A Novel Synthesis of Selenides and Selenol Esters Using
Liquid-Liquid Phase-Transfer Catalysis
Toshio Takido a , Masaharu Toriyama a , Kentaro Yamashita a , Tomoyuki Suwa a & Manabu
Seno a
a Nihon University , Tokyo, Japan
Published online: 27 Oct 2010.
To cite this article: Toshio Takido , Masaharu Toriyama , Kentaro Yamashita , Tomoyuki Suwa & Manabu Seno (2003) A Novel
Synthesis of Selenides and Selenol Esters Using Liquid-Liquid Phase-Transfer Catalysis, Phosphorus, Sulfur, and Silicon and the
Related Elements, 178:2, 319-326, DOI: 10.1080/10426500307940
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Phosphorus, Sulfur and Silicon, 2003, Vol. 178:319–326
C
Copyright 2003 Taylor & Francis
1042-6507/03 $12.00 + .00
DOI: 10.1080/10426500390170444
A NOVEL SYNTHESIS OF SELENIDES AND
SELENOL ESTERS USING LIQUID-LIQUID
PHASE-TRANSFER CATALYSIS
Toshio Takido, Masaharu Toriyama, Kentaro Yamashita,
Tomoyuki Suwa, and Manabu Seno
Nihon University, Tokyo, Japan
(Received March 22, 2002; accepted May 30, 2002)
This article describes the first attempt to synthesize selenides and
selenol esters prepared from the reaction of 1-benzyl or 1-acyl-
selenophenylmethaniminium halides and organic halides under
liquid-liquid phase-transfer conditions. This method also can be ap-
plied to the synthesis of diseleno tweezers-like molecules as metallore-
ceptors.
Keywords: Phase-transfer catalysis; selenides; selenium; selenobenza-
mide; selenol esters
12
Many different methods1
for preparing selenides and selenol es-
ters have been reported because functionalized organic selenium
compounds show wide applicability in synthetic organic chemistry.
Selenides are able to afford ylide derivatives13 which are important in-
termediates in organic synthesis, and selenol esters are used not only
16
as useful acylating agents,14
but afford carboxylic acids,17 ester,17
aldehydes,18 ketones,19,20 and amides21 as well. However, conventional
methods for the preparation of selenides and selenol esters often have
suffered from cumbersome manipulations and have sometimes involved
the use of toxic and malodorous compounds such as hydrogen selenide.
We previously have reported22,23 an efficient method of synthesiz-
ing sulfides and thiol esters using 1-alkyl or 1-acylthioethaniminium
halides as a source of alkanethiolate or thiocarboxylate ions. In an
extension of this work, this article describes the novel synthesis
of selenides and selenol esters from the reaction of 1-benzyl or 1-
acylselenophenylmethaniminium halides prepared by alkylation or
Address correspondence to Toshio Takido, Department of Mechanical and Applied
Chemistry, College of Science and Technology, Nihon University, Kanda Surugadai,
Chiyoda-Ku, Tokyo 101-8308, Japan. E-mail: takido@chem.cst.nihon-jp
319

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T . Takido et al.
acylation of selenobenzamide used as a source of selenolate ions and
organic halides under liquid-liquid phase-transfer conditions.
RESULTS AND DISCUSSION
In our present method, 1-benzylselenophenylmethaniminium bromide,
3, prepared from selenobenzamide,24 1, and benzyl bromide, 2, reacted
with corresponding organic halides, 4, to give an asymmetrical benzyl
selenide, 5, in a liquid-liquid two phase system consisting of benzene, a
sodium hydroxide aqueous solution, and a catalytic amount of a quar-
ternary ammonium salt as a phase transfer catalyst.
SCHEME 1
The reactions were carried out under mild conditions (30 C, 15 min),
and benzyl selenides and selenol esters, 5, were obtained in 59–94%
yields and the results are summarized in Table I. The reaction did not
proceed in the absence of a phase transfer catalyst under otherwise
identical conditions. These results were in complete contrast to the
synthesis of thiol esters. As reported before, 1-alkylthioethaniminium
bromides reacted with acyl halides to form the corresponding thiol es-
ters under similar conditions, however, the corresponding reaction af-
forded no thiol esters but rather N-acylthioimino esters as the main
products.22 This result suggests that the iminium carbon-selenium
likage of 3 is weaker than the iminium carbon-sulfur linkage of
1-alkylthioethaniminium bromides in alkaline solution. The attempts
to apply various kinds of alkyl and aryl halides in this reaction were ex-
amined. It was found that primary alkyl, secondary alkyl, allyl, and aryl
halides having electron withdrawing groups such as o- or p-substituted
nitrophenyl halides could be prepared, as opposed to tertiary alkyl and
other aryl halides.

321

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T . Takido et al.
The attempts to isolate the 1-alkyl or 1-acylselenophenylmeth-
animinium halides were unsuccessful due to their instability in air
while 1-benzylselenophenylmethaniminium bromide, 3, was success-
fully prepared. It is therefore reasonable to assume that the prepara-
tion of selenol esters by means of a one-pot reaction would be effective
as a synthetic strategy.
SCHEME 2
1-Acylselenophenylmethaniminium halides 7 prepared by the reac-
tion of 1 and acyl chlorides 6 in benzene were allowed to react with
corresponding alkyl bromides 8 in a phase transfer system without iso-
lation, the results of which are summarized in Table II. Furthermore,
the comparative reaction of 1-octanoylselenophenylmethaniminium
chloride with octyl bromide, and 1-octylselenophenylmethaniminium
bromide with octanoyl chloride under similar conditions were exam-
ined; it was found that the former reaction gave 1-octanoyl octanese-
lenoate 9f as the main product in 71% yield and the latter gave it in
57% yield respectively. This result would suggest that the rate of for-
mation of 1-acylselenophenylmethaniminium halides are faster than
that of 1-alkylselenophenylmethaniminium halides. In spite of the fact
that selenol esters are easily hydrolyzed in alkaline media, the prod-
ucts were not hydrolyzed as seen in the case of thiol ester synthesis,23
which produced selenol esters 9 in 52–88% yields.
We also have attempted to prepare 1,3-bis[(selenobenzyl)methyl]-
benzene 11 by the reaction of m-xylenebis[(selenophenyl)methan]-
iminium bromide 10 and benzyl bromide 2. The synthesis of diseleno
tweezers-like ligands such as 11 recently have begun to attract no-
tice because they have the ability of cyclometalation with a metal such

323

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T . Takido et al.
as Pt(II) as functionalized metalloreceptors.25 Our present method af-
forded a good yield (88%) of pure 11, using very little purification.
SCHEME 3
As far as we know, this is the first example of the syntheses of se-
lenides and selenol esters in selenium chemistry using selenoiminium
salt. This method does not use harmful or malodorous compounds and
can be widely applied to the synthesis of selenides and selenol esters.
EXPERIMENTAL
Selenobenzamide24 1 used for the synthesis of 3, 7, and 10 was prepared
by the procedure reported previously. The other reagents were commer-
cially available chemicals. Melting points were determined on Yanako
Micro melting point apparatus and are uncorrected. Boiling points are
uncorrected. Mass spectra were recorded on a HITACHI M-80B spec-
trometer. NMR spectra were recorded on JEOL GX-400.
1-Benzylselenophenylmethaniminium Bromide 3:
Typical Procedure
A mixture of selenobenzamide 1 (2.76 g, 15 mmol) and benzyl bromide
2 (2.565 g, 15 mmol) in chloroform (25 mL) was heated under reflux
for 30 min. After cooling, the precipitate was collected by filtration and
washed with diethyl ether to give 3 (5.01 g, 94%) as a colorless solid
of m.p. 144–145 C. IR (KBr) cm 1: 2894, 1607, 754. Anal. Calcd for
C14H14BrNSe: C, 47.34; H, 3.85; N, 3.95. Found: C, 47.10; H, 3.86; N,
4.00.
Benzyl Selenides and Selenol Esters 5:
General Procedure
A mixture of 1-benzylselenophenylmethaniminium bromide 3 (3.55 g,
10 mmol), organic halides 4 (10 mmol), tetrabutylammonium bromide

A Novel Synthesis of Selenides and Selenol Esters
325
(TBAB; 0.10 g, 0.3 mmol), benzene (50 mL) and sodium hydroxide
aqueous solution (30 wt% 50 g) were vigorously stirred at 30 C for
15 min. The organic layer was separated, washed with water, dried
over Na2SO4, and evaporated to dryness in vacuo to give a residue,
which was distilled under reduced pressure or recrystallized to give
pure unsymmetrical selenides 5.
Selenol Esters 9 by One-Pot Reaction; General Procedure
A mixture of selenobenzamide 1 (1.84 g, 10 mmol) and acyl halides
6 (10 mmol) in benzene (50 mL) was stirred at 30 C for 2 h under
nitrogen atmosphere. Then, alkyl halides 8 (10 mmol), TBAB (0.10 g,
0.3 mmol) and sodium hydroxide aqueous solution (30 wt% 50 g) were
added successively to the reaction mixture, and the whole was stirred
at 30 C for 3 h. The organic layer was separated, washed with water,
dried over Na2SO4, and evaporated to dryness in vacuo to give a residue,
which was distilled under reduced pressure or recrystallized to give
pure selenol esters 9.
Synthesis of 1,3-Bis[(selenobenzyl)methyl]benzene 11
A mixture of freshly prepared m-xylenebis[(selenophenyl)methan]
iminium bromide 10 (4.43 g, 7 mmol), benzyl bromide 2 (2.39 g,
14 mmol), TBAB (0.20 g, 0.6 mmol), benzene (40 mL), and sodium hy-
droxide aqueous solution (20 wt% 30 g) were heated under reflux for
1 h. The organic layer was separated, washed with water, dried over
Mg2SO4, and evaporated to dryness in vacuo to give a residue, which
was dried by heating under reduced pressure due to the removal of re-
maining benzyl bromide, and 11 was obtained as a pale yellow solid of
mp 37–39 C in 88% yield. This sample was sufficiently pure without
further purification. 1H-NMR (ppm): 3.66 (4H, s, CH2 2), 3.70 (4H,
s, CH2 2), 7.00–7.33 (14H, m, aromatic H). 13C-NMR (ppm): 27.40,
27.54, 126.56, 127.22, 128.34, 128.46, 128.84, 129.45, 138.96, 139.24.
HR-MS m/z: 447.0130(M+) (Calcd for C22H23Se2: 447.0125).
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