Synthesis of unsymmetrical diarylselenides from arylselenium complexes of titanocene and diaryl iodonium salts

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SYNTHESIS OF UNSYMMETRICAL DIARYLSELENIDES
FROM ARYLSELENIUM COMPLEXES OF TITANOCENE
AND DIARYL IODONIUM SALTS
a
a
b
Xiang Huang , Lu-Ling Wu & Xin-Hua Xu
a
Department of Chemistry , Zhejiang University , Xixi Campus, Hangzhou, 310028, P.R.
China
b
College of Chemical Engineering, Zhejiang University of Technology , Hangzhou,
10032, P.R. China
3
Published online: 16 Aug 2006.
To cite this article: Xiang Huang , Lu-Ling Wu & Xin-Hua Xu (2001) SYNTHESIS OF UNSYMMETRICAL DIARYLSELENIDES FROM
ARYLSELENIUM COMPLEXES OF TITANOCENE AND DIARYL IODONIUM SALTS, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 31:12, 1871-1874, DOI: 10.1081/SCC-100104337
To link to this article: http://dx.doi.org/10.1081/SCC-100104337
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SYNTHETIC COMMUNICATIONS, 31(12), 1871–1874 (2001)
SYNTHESIS OF UNSYMMETRICAL
DIARYLSELENIDES FROM
ARYLSELENIUM COMPLEXES
OF TITANOCENE AND DIARYL
IODONIUM SALTS
2
Xiang Huang, Lu-Ling Wu, and Xin-Hua Xu
,*
2
1
1
College of Chemical Engineering, Zhejiang University of
Technology, Hangzhou, 310032, P.R. China
2
Department of Chemistry, Zhejiang University, Xixi Campus,
Hangzhou, 310028, P.R. China
Diary selenides are important intermediates and a variety of synthetic routes
to unsymmetrical diaryl selenides are available. They include the reactions
1
of diazonium salts with alkali aryselenoates, diaryl deselenides with
2
Grignard reagents, arylselenium bromide with diaryl mercurical,
3
copper(I) or nickel(II) catalyzed arylation of areneseslenoates by aryl
4
5
iodides or bromides, aryl arylzo sulfones with alkaline areneselenoates,
arylselenation of electron-rich aromatic compounds with (phenylseleno)-
6
dimethylsulfonium tetrafluoroborate and photo-stimulated SRN1 reaction
7
of phenyl selenides with haloarenes. However, some of these methods suffer
from disadvantages such as the use of expensive or less easily available
reagents, harsh reaction conditions or lower yields. We now report a new
method for the synthesis of unsymmetrical diarylselenides.
8
We recently found that titanocene hydride (Cp TiH) generated from the
2
reaction of Cp TiCl with i-BuMgBr under mild conditions, readily reduced
2
2
diaryldiselenides to yield the corresponding arylselenium complexes of titano-
cene (Cp TiSeAr). They can be isolated and stored in THF for a month under
2
*
Corresponding author.
1
871
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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1
872
HUANG, WU, AND XU
nitrogen at room temperature. Cp TiSeAr has good nucleophilicity and can be
2
thought as an equivalent of arylselenenyl anion. We have reported that they
reacted with acyl halides or anhydrides to afford a convenient method for the
9
synthesis of selenoesters. In this paper we tried to study its reactivity with
haloarenes. However, the experiment showed that they cannot react with
haloarenes smoothly. Considering that diaryl iodonium salt is high reactive
arylating reagent, which can be regarded as an equivalent of aryl cation, we
study the reaction of Cp TiSeAr with diaryl iodonium salts. The experiment
2
showed that Cp TiSeAr reacted readily with diaryliodonium salts in THF/
2
ꢀ
HMPA at 60 C to give the unsymmetrical diaryl selenides in high yields. The
results are summarized in Table I.
The above method provides a new path for the synthesis of unsymme-
trical diarylselenides. Moreover, it has the advantages of simple procedure,
mild reaction conditions and good yields.
Table I. Unsymmetrical Diaryl Selenides (3a-f )
1
ꢀ
Product
Ar
Ar
M.p. C(lit.)
Yield (%)
3a
3b
3c
3d
3e
3f
p-CH
m-CH C H
3
C
6
H
4
Ph
Ph
Ph
Ph
oil
oil
oil
oil
78
70
73
69
75
75
3
6
4
p-CH
p-ClC
p-ClC H
3
OC
6
H
4
H
6 4
1
0
0
p-CH C H
6
71–72(72–73)
77–79(80–81)
6
4
3
4
1
p-BrC
6
H
4
p-CH
3
C
6
H
4
*
Yields based on 1.
EXPERIMENTAL
H NMR spectra were recorded on AZ-300 spectrometer, using CDCl3
1
as the solvent with TMS as internal standard. IR spectra were determined
on PE-683 spectrophotometer. Melting point are uncorrected. Tetra-

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UNSYMMETRICAL DIARYLSELENIDES
1873
hydrofuran was distilled from sodium benzophenone. Commercial HMPA
was dried over calcium hydride, distilled in vacuo and stored over 4A mol-
ecular sieves. All reactions were carried out under nitrogen.
Typical Procedure for the Synthesis of Arylselenium Complexes of
Titanocene (2): To the suspension of 2.5 g (10 mmol) of finely ground
titanocene dichloride in 50 ml THF was added a THF solution of
ꢀ
i-BuMgBr (1.0 M, 20 ml) for 30 minutes under stirring at À10 C. The reac-
tion mixture turned blackish-brown with a complete dissolution of titano-
cene and was further stirred 20 minutes at 0 C. The diaryldiselenide
ꢀ
(
5.0 mmol) was added to the reaction mixture. The solution immediately
became deep blue. The mixture was stirred for 1 hour at room temperature.
This solution was stored at room temperature under a positive pressure of
pure nitrogen and used in the preparation of unsymmetrical diarylselenides.
A Representative Procedure for the Synthesis of Unsymmetrical
Diarylselenides (3a–f ): To a solution of the diaryliodonium salt (1.0 mmol)
in 2.0 ml HMPA was added 5.0 ml (1.0 mmol) of Cp TiSeAr solution in
2
THF by syringe. The mixture was stirred at room temperature for 30 min-
ꢀ
utes, then stirred further for 2 h at 60 C, finally the deep blue disappeared
completely and the mixture turned red-brown. The reaction mixture was
diluted with dilute aqueous HCl (20 ml), and the aqueous layer was
extracted with ether (3 Â 20 ml). The combined organic phase was washed
with a saturated aqueous Na CO solution and brine and dried (MgSO )
2
3
4
and the solvent was evaporated. The residue was subjected to preparative
TLC on silica gel using light petroleum-ether as eluent (30:1).
4
-Methylphenyl phenyl selenide 3a: IR(film): 3080, 2930, 1580, 1480,
1
À1
1
440, 1060, 1020, 800, 730, 685, 660 cm
;
.10–7.51 (m, 9H); Calcd. for C H Se: C, 63.16, H, 4.89. Found: C, 63.20,
H NMR: d 2.28 (s, 3H),
7
H, 4.87.
13 12
3
-Methylphenyl phenyl selenide 3b: IR(film): 3075, 2930, 1580, 1480,
À1
1
1
445, 1060, 1020, 1090, 830, 770, 730, 680 cm ; H NMR: d 2.30 (s, 3H),
7.07–7.60 (m, 9H); Calcd. for C H Se: C, 63.16, H, 4.89. Found: C, 63.14,
H, 4.85.
1
3
12
4
-Methoxyphenyl phenyl selenide 3c: IR(film): 3085, 2885, 1605, 1495,
À1
1
1
480, 1250 cm ; H NMR: d 3.73 (s, 3H), 7.13–7.42 (m, 5H); Calcd. for
C H OSe: C, 59.32, H, 4.60. Found: C, 59.50, H, 4.56.
1
3
12
4
-Chlorophenyl phenyl selenide 3d: IR(film): 3080, 2930, 1680, 1480,
À1
1
1
440, 1390, 1090, 1010, 810, 730, 685 cm ; H NMR: d 7.12–7.61 (m);
Calcd. for C H ClSe: C, 53.86, H, 3.39. Found: C, 53.75, H, 3.32.
1
2
9
4
-Chlorophenyl 4-methylphenyl selenide 3e: IR(film): 3080, 2930,
À1
1
1
495, 1475, 1390, 1250, 1090, 1010, 810 cm ; H NMR: d 2.29 (s, 3H),
7.05–7.45 (m, 8H).

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1
874
HUANG, WU, AND XU
-Bromophenyl 4-methylphenyl selenide 3f: IR(film): 3080, 2930, 2860,
4
À1
1
1
495, 1475, 1390, 1070, 1010, 810 cm ; H NMR: d 2.28 (s, 3H), 6.91–7.30
(
m, 8H).
ACKNOWLEDGMENT
Project 29672008 was supported by National Nature Science
Foundation of China.
REFERENCES
1
2
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3
4
. Osuka, A.; Ohmasa, N. and Suzuki, H. Synthesis 1982, 857.
. Cristau, H.J.; Chabaud, B.; Labaudiniere, R. and Christol, E.
Organometallics 1985, 4, 657.
5. Evera, M.J.; Christiaens, L.E. and Renson, M.J. J. Org. Chem. 1986,
51, 5196.
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9
. Gassman, P.G.; Miura, A. and Miura, T. ibid. 1982, 47, 951.
. Pierini, A.B. and Rossi, R.A. ibid. 1979, 44, 4667.
. Gao, Y. and Sato, F. Chem. Commun. 1995, 659.
. XU, X.-H. and Huang, X. Synth. Commun. 1997, 27, 3797.
10. Greenberg, B.; Gould, E.S. and Burlant, W. J. Am. Chem. Soc. 1956,
78, 4028.
Received in the USA August 30, 2000

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