An efficient catalyst for ring opening of epoxides with phenol and thiophenol under solvent-free conditions

Article abstract of DOI:10.1016/j.tet.2013.10.098

An efficient and rapid procedure for ring opening reaction of various epoxides with phenol and thiophenol derivatives was developed. The procedure can be obtained at room temperature under solvent-free condition in presence of (C₄H₁₂N₂)₂[BiCl₆] Cl·H₂O (1 mol %). This catalyst can be reused several times without significant loss of activity.

Full text of DOI:10.1016/j.tet.2013.10.098

Accepted Manuscript
An efficient catalyst for ring opening of epoxides with phenol and thiophenol under
solvent-free conditions
Hong-fei Lu, Jun-tao Zhou, He-long Cheng, Lei-lei Sun, Fei-fei Yang, Run-ze Wu, Yu-
hua Gao, Zhi-bin Luo
PII:
S0040-4020(13)01659-1
10.1016/j.tet.2013.10.098
TET 24974
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 24 May 2013
Revised Date: 15 October 2013
Accepted Date: 27 October 2013
Please cite this article as: Lu H-f, Zhou J-t, Cheng H-l, Sun L-l, Yang F-f, Wu R-z, Gao Y-h, Luo Z-b, An
efficient catalyst for ring opening of epoxides with phenol and thiophenol under solvent-free conditions,
Tetrahedron (2013), doi: 10.1016/j.tet.2013.10.098.
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ACCEPTED MANUSCRIPT
Graphical Abstract
An efficient catalyst for ring opening of epoxides with phenol
and thiophenol under solvent-free conditions
a,
a
a
a
a
Hong-fei Lu *, Jun-tao Zhou , He-long Cheng , Lei-lei Sun , Fei-fei Yang , Run-ze
a
a
b,
Wu , Yu-hua Gao , Zhi-bin Luo *
School of Biology and Chemical Engineering, Jiangsu University of Science and
Technology, Zhenjiang, China
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang,
China
a
b
*
E-mail: zjluhf1979@hotmail.com
We introduce an efficient and rapid procedure for ring opening reaction of various
epoxides with phenol and thiophenol derivatives is developed at room temperature
under solvent-free condition in the presence of (C H N ) [BiCl ]Cl•H O(1 mol %).
4 12 2 2 6 2
This catalyst can be reused several times without significant losing of its activity.
1

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2
An efficient catalyst for ring opening of epoxides with phenol
and thiophenol under solvent-free conditions
a ,
a
a
a
a
3
4
5
6
7
8
Hong-fei Lu *, Jun-tao Zhou , He-long Cheng , Lei-lei Sun , Fei-fei Yang , Run-ze
a
a
b,
Wu , Yu-hua Gao , Zhi-bin Luo *
School of Biology and Chemical Engineering, Jiangsu University of Science and
Technology, Zhenjiang, China
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang,
China
a
b
9
0
1
2
3
Abstract: An efficient and rapid procedure for ring opening reaction of various
epoxides with phenol and thiophenol derivatives was developed. The procedure can
be obtained at room temperature under solvent-free condition in presence of
(C H N ) [BiCl ]Cl·H O (1 mol %). This catalyst can be reused several times
4 12 2 2 6 2
without significant loss of activity.
1
1
1
1
1
1
4
5
Keywords: Epoxides, Complex catalysis, Alcoholysis, Thiolysis
1. Introduction
[
1,2]
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6
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9
0
1
2
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Epoxides are versatile and important intermediates in organic synthesis.
Nucleophile-involved epoxide ring opening reaction is of great importance in organic
synthesis, since the reaction could offer a suitable route to get various kinds of
β-substituted alcohols for different uses. Therefore, how to develop a new catalyst
and to improve the performance of the epoxide ring opening reaction have drawn an
increasing attention. There have already been several references related to the ring
opening of epoxides with alcohols, thiols and amines, these reactions are mostly
[
3]
[4-7]
[8]
catalyzed by Lewis acids (BiCl , FeCl , SnCl , and Al(OTf) ,)
, alumina, metal
, and silica gel . Some examples of ring opening of epoxides under
3
[14]
3
4
3
[9-13]
complexes
[15-19]
mild conditions are also reported.
2
2
2
2
3
3
6
7
8
9
0
1
However, there are still many problems in these reported catalysis methods such
as the use of expensive reagents, catalyst activation difficulty, long reaction time, low
selectivity, environmental hazards, and catalyst recycling problem. Therefore, the
introduction of new methods for the nucleophilic-involved epoxides ring-opening,
which could proceed under mild conditions, is still in demand and important for
synthetic organic chemistry.
[
20]
3
3
3
3
3
2
3
4
5
6
In our preliminary work, we used (C H N ) [BiCl ]Cl·H O
(Fig.1, 2) to
4
12 2 2
6
2
[
21]
catalyze aminolysis of epoxides, and got a satisfied effect. In order to indicate the
extensive applicability of this catalyst, herein we investigated the ring opening
reaction of epoxides with phenol and thiophenol derivatives under this reaction
system. (Scheme 1, 2)
*Corresponding authors. Tel./fax: +86 511 84401181; e-mail address: zjluhf1979@hotmail.com
(Hong-fei Lu), zhibinluo@hotmail.com (Zhi-bin Luo)
1

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7
2. Results and discussion
3
3
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4
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4
4
4
4
5
5
8
9
0
1
2
3
4
5
6
7
8
9
0
1
Firstly, the reaction of phenolic derivatives with aliphatic mono-substituted
epoxides was examined. The predominant product was observed through the attack of
the hydroxy on the less hindered carbon of the compound, such as epoxypropane and
phenyl glycidyl ether, the reaction provided over 80% yield of the desired product
within 10 min (Table 1, entries 1–5, 16-18). The possible reason was that steric effect
predominated over electronic effect. However, in the reaction of phenolic derivatives
with epoxyethylbenzene, the predominant attacking position of hydroxy was the
benzylic position (Table 1, entries 6-8). We proposed that electronic effect
predominated over steric effect in this reaction procedure. In the case of cyclohexene
oxide and cyclopentene oxide, the reaction was generalized to phenolic derivatives,
thus only the trans-isomer was formed (Table 1, entries 9-15). On the other hand, in
the reaction of epoxides with p-chlorophenol, we obtained a relative lower yield, and
the reason may lay in that the p-electron-withdrawing Cl group could decrease the
reactivity of the nucleophile.
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a
5
2
Table 1 Ring opening of epoxides with phenol
b
c
Phenol and
thiophenol
Time Ratio
(min) (A:B)
Yield
(%)
Entry
1
Epoxide
Product
10
10
89:11
92:8
91
84
2
a
1a
3aa
3ab
2
3
1a
2b
1a
10
88:12
85
2
c
3
ac
OH
Cl
4
5
1a
1a
10
10
94:6
92:8
82
83
2
d
3ad
2
e
3
ae
6
7
10
10
0:100
0:100
90
85
2
a
1
b
3
ba
1b
1b
2b
3bb
8
9
10
10
5:95
82
87
2
e
3
be
-
1
c
2a
3
ca
3

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OH
1
0
1
1c
1c
10
10
-
-
83
81
Cl
3cd
2
d
1
2
e
3
ce
1
1
1
1
1
1
1
2
3
4
5
6
7
8
10
10
10
10
10
10
10
-
-
85
83
84
81
87
86
84
1
d
2a
3
da
1d
1d
1d
2b
3db
-
2
c
3
dc
OH
Cl
-
2
d
a
3dd
O
O
99:1
99:1
98:2
OH
2
1
g
3ga
CH3
O
O
1g
1g
OH
2b
3gb
OH
Cl
2
d
3gd
a
b
c
5
5
5
5
3
4
5
6
Epoxide (1.1 mmol), phenol (1.0 mmol), (C
4
12
H N
2
)
2
[BiCl
6 2
]Cl·H O (0.01 mmol)
1
Determined by H NMR
Isolated yield
5
5
5
7
8
9
4 12 2 2 6 2
To demonstrate whether (C H N ) [BiCl ]Cl·H O was also appropriate for the
ring opening reaction of epoxides with other nucleophile, thiophenol derivatives were
selected as nucleophile. The experimental results were well summarized in Table 2.
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The reaction mechanism of thiolysis was similar to alcoholysis. For styrene derived
epoxides, the major product was obtained as benzylic attack of the nucleophile. For
aliphatic alkene derived epoxides, the nucleophilic attack was occurred on the less
hindered carbon of the compound.
a
6
4
Table 2 Ring opening of epoxides with thiophenol
b
c
Phenol and
thiophenol
Time Ratio
(min) (A:B)
Yield
(%)
Entry
1
Epoxide
Product
10
10
93:7
80
4
a
1a
5aa
SH
H C
CH3
3
2
3
4
5
1a
1a
88:12
76
4
c
5
ac
10
10
10
100:0
0:100
0:100
79
75
79
4
d
5ad
SH
H C
CH3
3
1
b
4c
5
bc
S
HO
CH3
CH3
1b
5bd
4
d
5

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7
10
10
-
-
82
84
4
4
a
1
c
5ca
5cb
1c
b
SH
H C
CH3
3
8
9
1c
10
-
73
4
c
5
cc
10
10
-
-
80
83
1d
4
a
b
5da
1
0
1d
1d
4
5db
SH
H C
CH3
3
11
10
-
78
4
c
5
dc
1
1
2
3
1d
10
10
-
81
80
5dd
4
d
100:0
4
4
a
1
e
5ea
5eb
1
1
4
5
1e
1e
10
10
100:0
100:0
80
73
b
SH
H C
CH3
3
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c
5ec
1
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1
6
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8
1e
10
10
10
100:0
93:7
92:8
76
79
75
4
d
5
ed
1
f
4
b
5fb
OH
CH3
SH
S
H C
CH3
3
ClH C
2
1f
H C
3
4
c
5fc
1
2
9
0
10
10
100:0
100:0
83
81
4
4
a
1
g
5ga
1g
b
5gb
a
b
c
6
6
6
6
5
6
7
8
Epoxide (1.1 mmol), thiophenol (1.0 mmol), (C
4
12
H N
2
) [BiCl
2
6
2
]Cl·H O (0.01 mmol)
1
Determined by H NMR
Isolated yield
6
7
7
7
7
7
7
7
9
0
1
2
3
4
5
6
The reaction of cyclohexene oxide with p-chlorothiophenol was then chosen as a
model reaction to explore the influence of catalysts. Under solvent-free condition,
only the catalysts (C [FeCl ]Cl·H O and (C [BiCl ]Cl·H O could
provide excellent yields within short reaction time (10 min) under ambient
temperature. Besides, only trans-isomer (Table 3, entries1–7) was generated. Other
kinds of catalysts utilized in the reaction either suffered from low reaction yield or
long reaction time, which demonstrated that our selected catalyst system is much
more suitable for this kind of reaction.
4
H
12
N
2
)
2
6
2
4
H
12
N
2
)
2
6
2
7
7
7
8
a
Table 3 Ring opening of epoxides with different catalysts
b
Entry
Catalyst
Solvent
Time
Yield (%)
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1
2
3
4
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7
None
BiCl
[FeCl
(C H N ) [MnCl ]Cl·H O
solvent-free
solvent-free
solvent-free
solvent-free
solvent-free
solvent-free
solvent-free
24h
12h
9
3
55
85
43
82
69
61
(C
4
H
12
N
2
)
2
6
]Cl·H
2
O
10 min
10 min
10 min
10 min
10 min
4
12 2 2
4
2
(C
(C
(C
4
H
12
N
2
)
2
[BiCl
[NiCl
[SbCl
6
]Cl·H
]Cl·H
]Cl·H
2
O
2
O
2
O
4
H
H
12
N
2
)
2
6
4
12
N
2
)
2
6
a
7
8
8
9
0
1
Reaction conditions: cyclohexene oxide (1.1 mmol), thiophenol (1.0 mmol), catalyst (0.01
mmol), 10 min, room temperature
b
Isolated yield
8
8
8
8
8
8
2
3
4
5
6
7
In the reaction of cyclohexene oxide with p-chlorothiophenol, the catalyst
(C H N ) [FeCl ]Cl·H O
showed
O. But when the nucleophile was changed to phenol, much
[BiCl ]Cl·H O was chosen as catalyst.
O was selected as the catalyst in the following
similar
catalytic
activity
as
4
12 2 2
6
2
(C
4
H N ) [BiCl ]Cl·H
12 2 2 6 2
better results were obtained if (C
Therefore, (C [BiCl ]Cl·H
reaction process. (Scheme 3)
4
H
12
N
2
)
2
6
2
4
H
12
N
2
)
2
6
2
8
8
8
9
9
9
0
1
In fact, the actual mechanism of these Bi complex catalyzed reactions are not
clear at present. However, the favorable performance of this kind of catalyst prompted
us to present a possible mechanistic pathway. As shown in Fig.3.
8

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2
9
9
9
9
9
9
9
3
4
5
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7
8
9
Since catalyst recovery is a key factor of superior performance in catalysis
reactions, we utilized the reaction of cyclohexene oxide with 4-methyl thiophenol to
investigate the recovery times of catalyst (C H N ) [BiCl ]Cl·H O. After reaction,
4 12 2 2 6 2
the mixture was diluted by ethyl acetate and the catalyst was recovered from the
organic phase just by a simple filtration without further purification. As can be seen
from Fig.4, even after recycling for ten times, the catalyst can still remain high
activity, showing the practical application of the catalyst in related reactions.
1
00
80
60
40
20
0
1
2
3
4
5
6
7
8
9
10
Cycle
Fig.4 Recycling of catalyst (C H N ) [BiCl ]Cl H O
4
12 2 2
6
2
1
00
3. Conclusion
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In conclusion, a novel, mild, and efficient route to synthesis of β-functionalized
alcohols by ring opening of epoxides with phenol and thiophenol derivatives using
(C H N ) [BiCl ]Cl·H O as catalyst has been successfully developed. The specific
advantages of the reactions are as follow: solvent-free condition, short reaction time,
simple operation, high yield and reusable of the catalyst. We expect this new method
to be useful in more chemical applications.
4
12 2 2
6
2
1
1
07
08
4. Experimental
4.1 General information
1
1
1
1
1
1
1
09
10
11
12
13
14
15
All commercially available reagents were used without further purification.
Reaction progress was monitored with thin layer chromatography (TLC) performed
on GF254 silica gel plates. Column chromatography was performed with silica gel
1
200-300 mesh. All H NMR spectra were recorded in CDCl
3
solution and reported in
ppm (δ). 1H NMR spectra were referenced internally to the residual proton resonance
in CDCl (δ=7.26 ppm), or with tetramethylsilane (TMS, δ=0.00 ppm) as the internal
standard.
3
1
16
4.2 General procedure for the catalyst (C H N ) [BiCl ]Cl·H O
4 12 2 2 6 2
1
1
1
1
17
18
19
20
3
Piperazine (10 mmol 0.86 g), BiCl (6.8 mmol, 2.15 g) and 35% aqueous HCl (3
mL) were mixed and dissolved in 30 mL of water, heated to 353 K to form a clear
solution. The reaction mixture was cooled slowly to room temperature, block crystals
of the title compound was collected after fifteen days.
1
21
4.3 General procedure for ring opening of epoxides with phenol and thiophenol
1
1
1
1
1
1
1
1
22
23
24
25
26
27
28
29
A mixture of epoxide (1.1 mmol), phenol/thiophenol (1.0 mmol), and
(C H N ) [BiCl ]Cl·H O (0.01 mmol) was stirred in a flask. The course of the
4 12 2 2 6 2
reaction was monitored by TLC, complete disappearance of the raw materials was
observed within 10 min. The mixture was diluted by ethyl acetate (10 mL) and the
catalyst was separated from the organic phase by a simple filtration. The organic
phase was washed successively with aqueous NaHCO
anhydrous Na SO , and evaporated under reduced pressure to provide the crude
product, which was purified by column chromatography.
3
and water, dried over
2
4
[
26]
1
1
1
1
1
1
30
31
32
33
34
4.3.1. 1-phenoxypropan-2-ol (3aa)
3
Colorless oil; H NMR (300 MHz, CDCl ) δ
7.37–7.26 (m, 2H), 7.04–6.87 (m, 3H), 4.55 (m, J = 10.3, 5.2 Hz, 1H), 4.24 (m, J =
7.7, 6.4, 3.2 Hz, 1H), 3.98 (m, J = 9.3, 3.2 Hz, 1H), 3.88–3.76 (m, 1H), 2.05 (s, 1H),
1.32 (m, J = 6.3, 3.2 Hz, 3H). Anal. Calcd for C H O : C, 71.03; H, 7.95. Found: C,
9
12
2
71.26; H, 7.78.
[
28]
1
1
1
1
1
35
36
37
38
4.3.2. 1-(p-tolyloxy)propan-2-ol (3ab) Colorless oil; H NMR (300 MHz, CDCl ) δ
3
7.12 (d, J = 8.2 Hz, 2H), 6.90–6.81 (m, 2H), 4.21 (m, J = 12.9, 6.4, 3.2 Hz, 1H), 3.95
(m, J = 9.3, 3.1 Hz, 1H), 3.84–3.72 (m, 1H), 2.33 (s, 3H), 2.02 (s, 1H), 1.30 (t, J = 6.0
Hz, 3H). Anal. Calcd for C H O : C, 72.26; H, 8.49. Found: C, 71.39; H, 8.34.
10
14
2
[
28]
1
1
39
3
4.3.3. 1-(m-tolyloxy)propan-2-ol (3ac) Yellow oil; H NMR (300 MHz, CDCl ) δ
10

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1
1
1
40
41
42
7.20 (t, J = 7.7 Hz, 1H), 6.88–6.71 (m, 3H), 4.22 (m, J = 7.7, 6.4, 3.2 Hz, 1H), 3.97
(m, J = 9.3, 3.2 Hz, 1H), 3.88–3.72 (m, 1H), 2.37 (s, 3H), 1.31 (m, J = 6.3, 3.2 Hz,
3H). Anal. Calcd for C H O : C, 72.26; H, 8.49. Found: C, 71.88; H, 8.62.
1
0
14
2
1
1
1
1
1
1
43
44
45
46
47
4.3.4. 1-(naphthalen-1-yloxy)propan-2-ol (3ae) Colorless oil; H NMR (300 MHz,
CDCl ) δ 8.35 –8.24 (m, 1H), 7.89–7.80 (m, 1H), 7.58–7.46 (m, 3H), 7.41 (t, J = 7.9
3
Hz, 1H), 6.86 (d, J = 7.5 Hz, 1H), 4.47–4.34 (m, 1H), 4.16 (m, J = 9.3, 3.3 Hz, 1H),
4.05 (m, J = 9.3, 7.4 Hz, 1H), 2.45 (s, 1H), 1.42 (d, J = 6.4 Hz, 3H). Anal. Calcd for
13 14 2
C H O : C, 77.20; H, 6.98. Found: C, 77.58; H, 7.01.
[
22]
1
1
1
1
1
48
49
50
51
3
4.3.5. 2-phenoxy-2-phenylethanol (3ba) Colorless oil; H NMR (300 MHz, CDCl )
δ 7.42–7.28 (m, 6H), 7.28–7.18 (m, 2H), 7.00–6.85 (m, 3H), 5.31 (m, J = 8.1, 3.7 Hz,
1H), 3.91 (m, J = 15.6, 11.9, 5.9 Hz, 2H). Anal. Calcd for C H O : C, 78.48; H, 6.59.
1
4
14
1
2
Found: C, 78.04; H, 6.86.
[
30]
1
1
1
1
52
53
54
55
4.3.6. 2-phenyl-2-(p-tolyloxy)ethanol (3bb)
CDCl ) δ 7.45–7.27 (m, 5H), 7.03 (d, J = 8.3 Hz, 2H), 6.85–6.77 (m, 2H), 5.26 (m, J
3
= 8.1, 3.7 Hz, 1H), 3.89 (m, J = 15.6, 11.9, 5.9 Hz, 2H), 2.27 (s, 3H), 2.02 (s, 1H).
Anal. Calcd for C H O : C, 78.92; H, 7.06. Found: C, 78.65; H, 7.27.
Colorless oil; H NMR (300 MHz,
1
5
16
2
1
1
1
1
1
1
56
57
58
59
60
4.3.7. 2-(naphthalen-1-yloxy)-2-phenylethanol (3be) Colorless oil; H NMR (300
MHz, CDCl ) δ 8.24–8.14 (m, 1H), 7.78–7.67 (m, 1H), 7.48–7.38 (m, 4H), 7.36 (d, J
3
= 6.6 Hz, 2H), 7.33–7.22 (m, 3H), 6.73 (d, J = 7.6 Hz, 1H), 5.21 (d, J = 2.6 Hz, 1H),
4.26–4.11 (m, 2H), 2.72 (s, 1H). Anal. Calcd for C H O : C, 81.79; H, 6.10. Found:
18
16
2
C, 81.92; H, 6.02.
[
22]
1
1
1
1
1
1
61
62
63
64
65
4.3.8. trans-2-phenoxycyclohexanol (3ca)
Colorless oil; H NMR (300 MHz,
3
CDCl ) δ 7.33–7.27 (m, 1H), 7.15 (t, J = 7.7 Hz, 1H), 6.96 (t, J = 7.3 Hz, 2H), 6.74 (t,
J = 7.1 Hz, 1H), 4.05-3.94 (m, 1H), 3.77–3.67 (m, 1H), 2.14 (m, J = 14.5, 8.9 Hz, 2H),
1.84–1.72 (m, 2H), 1.45–1.22 (m, 4H). Anal. Calcd for C H O : C, 74.97; H, 8.39.
12
16
2
Found: C, 74.58; H, 8.56.
[
23]
1
1
1
1
1
1
66
67
68
69
70
4.3.9. trans-2-(4-chlorophenoxy)cyclohexanel (3cd)
Colorless oil; H NMR (300
3
MHz, CDCl ) δ 7.32–7.20 (m, 2H), 6.96–6.85 (m, 2H), 3.98 (m, J = 10.3, 8.4, 4.4 Hz,
1H), 3.74 (m, J = 10.4, 8.6, 4.6 Hz, 1H), 2.18–2.11 (m, 2H), 1.85–1.70 (m, 2H),
1.48–1.26 (m, 4H). Anal. Calcd for C H ClO : C, 63.58; H, 6.67. Found: C, 63.46;
H, 6.73.
4.3.10. trans-2-(naphthalen-1-yloxy)cyclohexanol (3ce) Yellow oil; H NMR (300
MHz, CDCl ) δ 8.30–8.22 (m, 1H), 7.84–7.76 (m, 1H), 7.53–7.46 (m, 2H), 7.45–7.33
(m, 2H), 6.95 (d, J = 7.4 Hz, 1H), 4.33–4.15 (m, 1H), 4.01–3.81 (m, 1H), 2.26–2.14
1
2
15
2
1
1
1
1
1
1
1
71
72
73
74
75
76
3
-1
(m, 2H), 1.78 (m, J = 6.0, 2.9 Hz, 2H), 1.48–1.35 (m, 4H). IR λmax (KBr, cm ) 3359.4,
3051.8, 2934.1, 2861.3, 1578.0, 1461.8, 1397.2, 1265.1, 1096.3, 769.9. Anal. Calcd
for C16H O : C, 79.31; H, 7.49. Found: C, 79.71; H, 7.31.
18 2
[
27]
1
1
1
1
77
78
79
4.3.11. trans-2-phenoxycyclopentanol (3da)
Colorless oil; H NMR (300 MHz,
CDCl ) δ 7.27 (m, J = 10.2, 5.6 Hz, 3H), 6.93 (t, J = 9.0 Hz, 3H), 4.53 (m, J = 6.3, 3.0
Hz, 1H), 4.33 (t, J = 6.5 Hz, 1H), 2.18 (m, J = 14.2, 6.3 Hz, 1H), 2.14–2.01 (m, 1H),
3
11

ACCEPTED MANUSCRIPT
1
1
80
81
1.89–1.72 (m, 3H), 1.70–1.57 (m, 3H). Anal. Calcd for C11
Found: C, 74.37; H, 8.04.
H
14
O
2
: C, 74.13; H, 7.92.
1
1
1
1
1
1
1
82
83
84
85
86
87
4.3.12. trans-2-(p-tolyloxy)cyclopentanol (3db) Colorless oil; H NMR (300 MHz,
3
CDCl ) δ 7.07 (d, J = 8.5 Hz, 2H), 6.81 (d, J = 8.5 Hz, 2H), 4.49 (m, J = 6.3, 3.0 Hz,
1H), 4.31 (m, J = 7.3, 5.8 Hz, 1H), 2.29 (s, 3H), 2.21 – 2.11 (m, 1H), 2.07–2.01 (m,
1H), 1.82 (d, J = 7.6 Hz, 3H), 1.78–1.70 (m, 1H), 1.65 (m, J = 15.7, 9.3, 4.3 Hz, 1H).
-1
IR λmax (KBr, cm ) 3343.9, 3029.1, 2842.3, 2875.3, 1613.6, 1507.6, 1231.8, 1037.9,
812.8. Anal. Calcd for C12
H
16
O
2
: C, 74.97; H, 8.39. Found: C, 75.25; H, 8.23.
1
1
1
1
1
1
88
89
90
91
92
4.3.13. trans-2-(m-tolyloxy)cyclopentanol (3dc) Colorless oil; H NMR (300 MHz,
3
CDCl ) δ 7.16 (t, J = 7.8 Hz, 1H), 6.83 – 6.69 (m, 4H), 4.51 (m, J = 6.5, 3.1 Hz, 1H),
4.31 (t, J = 6.4 Hz, 1H), 2.32 (s, 3H), 2.19 – 2.12 (m, 1H), 2.12 – 2.01 (m, 1H), 1.87 –
1.79 (m, 2H), 1.68 (s, 2H). Anal. Calcd for C H O : C, 74.97; H, 8.39. Found: C,
75.21; H, 8.04.
4.3.14. trans-2-(4-chlorophenoxy)cyclopentanol (3dd) Colorless oil; H NMR (300
MHz, CDCl ) δ 7.32–7.19 (m, 2H), 6.91–6.82 (m, 2H), 4.50 (m, J = 5.8, 2.9 Hz, 1H),
4.32 (m, J = 7.4, 5.6 Hz, 1H), 2.27–2.02 (m, 2H), 1.84 (m, J = 12.7, 7.1, 5.0 Hz, 2H),
12
16
2
1
1
1
1
1
1
93
94
95
96
97
3
1.76 (s, 1H), 1.74–1.63 (m, 1H). Anal. Calcd for C11
Found: C, 62.57; H, 6.42.
H13ClO
2
: C, 62.12; H, 6.16.
[
29]
1
1
1
2
2
98
99
00
01
4.3.15. 1,3-diphenoxypropan-2-ol (3ga) White solid, mp 74-76℃; H NMR (400
MHz, CDCl ) δ 7.32–7.26 (m, 4H), 6.95 (m, J = 19.3, 12.0 Hz, 6H), 4.43–4.36 (m,
1H), 4.20–4.11 (m, 4H), 2.57 (s, 1H). Anal. Calcd for C H O : C, 73.75; H, 6.60.
3
1
5
16
3
Found: C, 73.49; H, 6.48.
[
30]
1
2
2
2
2
02
03
04
05
4.3.16 1-phenoxy-3-(p-tolyloxy)propan-2-ol (3gb)
White solid, mp 57-59℃; H
NMR (400 MHz, CDCl
3H), 6.85–6.80 (m, 2H), 4.40–4.34 (m, 1H), 4.17–4.07 (m, 4H), 2.59 (s, 1H), 2.28 (s,
3H). Anal. Calcd for C16 : C, 74.39; H, 7.02. Found: C, 74.03; H, 7.68.
3
) δ 7.31–7.25 (m, 2H), 7.08 (d, J = 8.2 Hz, 2H), 6.99–6.90 (m,
18 3
H O
[
31]
2
2
2
2
06
07
08
09
4.3.17 1-(4-chlorophenoxy)-3-phenoxypropan-2-ol (3gd) White solid, mp 62-64℃;
1
3
H NMR (400 MHz, CDCl ) δ 7.32–7.26 (m, 2H), 7.25–7.20 (m, 2H), 7.01–6.89 (m,
3H), 6.88–6.81 (m, 2H), 4.36 (m, J = 10.5, 5.1 Hz, 1H), 4.18–4.06 (m, 4H), 2.73 (s,
1H). Anal. Calcd for C H ClO : C, 64.64; H, 5.42. Found: C, 64.97; H, 5.69.
1
5
15
3
[
25]
1
2
2
2
2
10
11
12
13
4.3.18. 1-((4-chlorophenyl)thio)propan-2-ol (5aa)
Colorless oil; H NMR (300
MHz, CDCl ) δ 7.31–7.25 (m, 4H), 3.85 (m, J = 8.5, 6.2, 3.7 Hz, 1H), 3.08 (m, J =
13.7, 3.7 Hz, 1H), 2.84 (m, J = 13.7, 8.4 Hz, 1H), 1.27 (d, J = 6.2 Hz, 3H). Anal.
Calcd for C H ClOS: C, 53.33; H, 5.47. Found: C, 53.62; H, 5.64.
3
9
11
1
2
2
2
2
14
15
16
17
4.3.19. 1-((2,6-dimethylphenyl)thio)propan-2-ol (5ac) Colorless oil; H NMR (300
MHz, CDCl ) δ 7.17–7.02 (m, 2H), 3.80–3.61 (m, 1H), 2.81 (m, J = 13.1, 3.6 Hz, 1H),
3
2.72–2.60 (m, 1H), 2.56 (s, 3H), 2.43 (s, 1H), 1.22 (d, J = 6.2 Hz, 2H). Anal. Calcd
for C H OS: C, 67.30; H, 8.22. Found: C, 66.97; H, 8.39.
11
16
1
2
2
18
19
4.3.20. 1-((4-isopropylphenyl)thio)propan-2-ol (5ad) Yellow oil; H NMR (400 MHz,
CDCl ) δ 7.34–7.30 (m, 2H), 7.17–7.13 (m, 2H), 3.81 (m, J = 12.4, 6.2, 3.7 Hz, 1H),
3
12

ACCEPTED MANUSCRIPT
2
2
2
2
20
21
22
23
3.06 (m, J = 13.7, 3.7 Hz, 1H), 2.87 (m, J = 13.9, 6.9 Hz, 1H), 2.79 (m, J = 13.7, 8.7
Hz, 1H), 2.39 (s, 1H), 1.25–1.22 (m, 6H), 1.21 (s, 3H). IR λmax (KBr, cm ) 3348.3,
3019.0, 2961.1, 1926.9, 2870.0, 1496.0, 1406.3, 1048.6, 816.7. Anal. Calcd for
-1
C
12
H
18OS: C, 68.52; H, 8.63. Found: C, 68.31; H, 8.49.
4.3.21. 2-((2,6-dimethylphenyl)thio)-2-phenylethanol (5bc) Colorless oil; H NMR
(300 MHz, CDCl ) δ 7.36–7.26 (m, 5H), 7.20–7.08 (m, 3H), 4.06–3.95 (m, 2H), 3.91
(td, J = 7.1, 2.9 Hz, 1H), 2.47 (s, 6H), 1.88 (s, 1H). Anal. Calcd for C H OS: C,
[24]
1
2
2
2
2
24
25
26
27
3
16
18
74.38; H, 7.02. Found: C, 74.46; H, 7.51.
4.3.22. 2-((4-isopropylphenyl)thio)-2-phenylethanol (5bd) Yellow oil; H NMR (400
MHz, CDCl ) δ 7.37 (t, J = 2.0 Hz, 1H), 7.35–7.31 (m, 5H), 7.27 (m, J = 8.5, 5.2, 2.7
1
2
2
2
2
2
2
28
29
30
31
32
33
3
Hz, 1H), 7.19 (d, J = 2.0 Hz, 1H), 7.16 (d, J = 1.6 Hz, 1H), 4.69 (m, J = 9.5, 3.5 Hz,
1H), 3.29 (m, J = 7.8, 3.5 Hz, 1H), 3.13–2.99 (m, 2H), 2.89 (m, J = 13.8, 6.9 Hz, 1H),
1.24 (d, J = 6.9 Hz, 6H). Anal. Calcd for C17H20OS: C, 74.96; H, 7.40. Found: C,
75.29; H, 7.31.
[
19]
1
2
2
2
2
2
34
35
36
37
38
4.3.23. trans-2-((4-chlorophenyl)thio)cyclohexanol (5ca)
Colorless oil; H NMR
(300 MHz, CDCl ) δ 7.38–7.29 (m, 2H), 7.29–7.19 (m, 2H), 3.25 (m, J = 10.0, 4.3 Hz,
1H), 2.79–2.60 (m, 1H), 2.09–1.96 (m, 2H), 1.65 (m, J = 10.8, 6.7, 2.7 Hz, 2H),
3
1.30–1.14 (m, 4H). Anal. Calcd for C12
H, 6.63.
H15ClOS: C, 59.37; H, 6.23. Found: C, 59.73;
[
22]
1
2
2
2
2
2
39
40
41
42
43
4.3.24. trans-2-(p-tolylthio)cyclohexanol (5cb)
Yellow oil; H NMR (300 MHz,
CDCl ) δ 7.37 (d, J = 8.1 Hz, 1H), 7.12 (d, J = 7.9 Hz, 1H), 3.38–3.19 (m, 1H),
2.76–2.60 (m, 1H), 2.34 (s, 2H), 2.17–2.02 (m, 1H), 1.69 (m, J = 8.2, 6.0, 2.8 Hz, 1H),
3
1.34–1.19 (m, 2H). Anal. Calcd for C13
8.51.
H
18OS: C, 70.22; H, 8.16. Found: C, 70.11; H,
1
2
2
2
2
2
2
44
45
46
47
48
49
4.3.25. trans-2-((2,6-dimethylphenyl)thio)cyclohexanol (5cc) Colorless oil; H NMR
(300 MHz, CDCl
3
) δ 7.12 (d, J = 2.7 Hz, 3H), 3.53 (m, J = 9.8, 4.5 Hz, 1H),
2.78–2.68 (m, 1H), 2.56 (s, 6H), 2.18–2.00 (m, 2H), 1.88 (m, J = 7.2, 3.6, 1.9 Hz, 2H),
1.39–1.22 (m, 4H). IR λmax (KBr, cm ) 3229.7, 3053.7, 2929.3, 2855.1, 1458.4,
-1
1328.2, 1064.5, 765.1. Anal. Calcd for C14
H, 8.48.
H20OS: C, 71.14; H, 8.53. Found: C, 71.33;
[
23]
1
2
2
2
2
2
50
51
52
53
54
4.3.26. trans-2-((4-chlorophenyl)thio)cyclopentanol (5da) Colorless oil; H NMR
(300 MHz, CDCl ) δ 7.41–7.33 (m, 2H), 7.32–7.25 (m, 2H), 4.13 (m, J = 10.5, 4.5 Hz,
3
1H), 3.40 (td, J = 7.1, 4.5 Hz, 1H), 2.30 (m, J = 13.5, 7.8, 5.5 Hz, 1H), 2.09 (m, J =
13.1, 8.3, 6.5 Hz, 1H), 1.80 (m, J = 10.3, 9.0, 6.4 Hz, 2H), 1.65 (m, J = 21.1, 11.6, 6.1
Hz, 2H). Anal. Calcd for C H ClOS: C, 57.76; H, 5.73. Found: C, 57.52; H, 5.85.
1
1
13
[
23]
1
2
2
2
2
2
55
56
57
58
59
4.3.27. trans-2-(p-tolylthio)cyclopentanol (5db) Colorless oil; H NMR (300 MHz,
CDCl ) δ 7.33 (d, J = 8.0 Hz, 2H), 7.11 (d, J = 7.9 Hz, 2H), 4.08 (m, J = 10.8, 4.9 Hz,
3
1H), 3.32 (m, J = 11.9, 7.1 Hz, 1H), 2.32 (s, 3H), 2.28–2.18 (m, 1H), 2.05 (m, J =
14.8, 6.5 Hz, 1H), 1.80–1.69 (m, 2H), 1.67–1.54 (m, 2H). Anal. Calcd for C H OS:
12
16
C, 69.19; H, 7.74. Found: C, 68.73; H, 7.66.
13

ACCEPTED MANUSCRIPT
1
2
2
2
2
2
60
61
62
63
64
4.3.28. trans-2-((2,6-dimethylphenyl)thio)cyclopentanol (5dc) Colorless oil; H NMR
(300 MHz, CDCl ) δ 7.16 – 7.07 (m, 3H), 4.03 (m, J = 10.7, 4.7 Hz, 1H), 3.15 (m, J =
11.6, 6.7 Hz, 1H), 2.56 (s, 6H), 2.19–2.07 (m, 2H), 1.84–1.70 (m, 2H), 1.59 (t, J = 7.0
Hz, 2H). IR λmax (KBr, cm ) 3342.0, 3054.1, 2953.4, 2871.0, 1458.9, 768.0. Anal.
Calcd for C13 18OS: C, 70.22; H, 8.16. Found: C, 70.51; H, 8.43.
3
-1
H
1
2
2
2
2
2
2
65
66
67
68
69
70
4.3.29. trans-2-((4-isopropylphenyl)thio)cyclopentanol (5dd) Colorless oil; H NMR
(300 MHz, CDCl ) δ 7.36 (d, J = 8.2 Hz, 2H), 7.16 (d, J = 8.2 Hz, 2H), 4.10 (m, J =
10.9, 4.9 Hz, 1H), 3.34 (m, J = 11.8, 7.2 Hz, 1H), 2.88 (m, J = 13.8, 6.9 Hz, 1H),
2.31–2.17 (m, 1H), 2.14–2.01 (m, 1H), 1.85–1.70 (m, 2H), 1.64–1.52 (m, 2H), 1.23 (d,
J = 6.9 Hz, 6H). IR λmax (KBr, cm ) 3363.2, 3018.0, 2958.3, 2858.6, 1495.5, 1405.8,
3
-1
818.6. Anal. Calcd for C14
H
20OS: C, 71.14; H, 8.53. Found: C, 70.52; H, 8.72.
1
2
2
2
2
71
72
73
74
4.3.30. 1-((4-chlorophenyl)thio)-2-methylpropan-2-ol (5ea) Colorless oil; H NMR
3
(300 MHz, CDCl ) δ 7.38 (d, J = 8.5 Hz, 2H), 7.28 (m, J = 8.2, 1.3 Hz, 2H), 3.13 (s,
2H), 2.21 (s, 1H), 1.34 (s, 6H). Anal. Calcd for C10
C, 55.39; H, 6.31.
H
13ClOS: C, 55.42; H, 6.05. Found:
1
2
2
2
75
76
77
4.3.31. 2-methyl-1-(p-tolylthio)propan-2-ol (5eb) Colorless oil; H NMR (300 MHz,
CDCl
3
) δ 7.32 (d, J = 8.1 Hz, 2H), 7.09 (d, J = 8.0 Hz, 2H), 3.08 (s, 2H), 2.31 (s, 3H),
16OS: C, 67.30; H, 8.22. Found: C, 67.51; H, 8.41.
1.29 (s, 6H) Anal. Calcd for C11
H
1
2
2
2
2
78
79
80
81
4.3.32. 1-((2,6-dimethylphenyl)thio)-2-methylpropan-2-ol (5ec) Colorless oil;
H
NMR (400 MHz, CDCl ) δ 7.15–7.06 (m, 3H), 2.83 (s, 2H), 2.56 (s, 6H), 2.40–2.31
(m, 1H), 1.30 (s, 6H). IR λmax (KBr, cm ) 3267.3, 3054.2, 2968.4, 2913.9, 1456.9,
3
-1
1205.8, 773.8. Anal. Calcd for C12
H
18OS: C, 68.52; H, 8.63. Found: C, 68.62; H, 8.78.
1
2
2
2
2
2
82
83
84
85
86
4.3.33. 1-((4-isopropylphenyl)thio)-2-methylpropan-2-ol (5ed) Colorless oil; H NMR
(400 MHz, CDCl
3
) δ 7.35 (d, J = 8.3 Hz, 2H), 7.14 (d, J = 8.2 Hz, 2H), 3.10 (s, 2H),
2.87 (m, J = 13.8, 6.9 Hz, 1H), 1.30 (s, 6H), 1.23 (d, J = 6.9 Hz, 6H). IR λ (KBr,
max
-1
cm ) 3346.8, 3076.9, 2969.8, 2927.1, 1379.3, 1045.7, 821.3. Anal. Calcd for
20OS: C, 69.59; H, 8.98. Found: C, 69.74; H, 8.53.
13
C H
[
25]
1
2
2
2
2
87
88
89
90
4.3.34. 1-chloro-3-(p-tolylthio)propan-2-ol (5fb) Yellow oil; H NMR (300 MHz,
CDCl ) δ 7.32 (d, J = 8.2 Hz, 1H), 7.12 (d, J = 7.9 Hz, 1H), 3.93–3.84 (m, 1H), 3.66
(m, J = 4.9, 2.5 Hz, 1H), 3.07 (m, J = 13.9, 6.3 Hz, 1H), 2.33 (s, 2H). Anal. Calcd for
3
C
10
H
13ClOS: C, 55.42; H, 6.05. Found: C, 55.21; H, 6.42.
4.3.35. 1-chloro-3-((2,6-dimethylphenyl)thio)propan-2-ol (5fc) Yellow oil; H NMR
(300 MHz, CDCl ) δ 7.21–7.11 (m, 3H), 3.84 (m, J = 10.6, 5.4 Hz, 1H), 3.69 (m, J =
11.2, 4.9 Hz, 2H), 2.98–2.82 (m, 2H), 2.59 (s, 6H). Anal. Calcd for C H ClOS: C,
57.25; H, 6.55. Found: C, 57.52; H, 6.23.
4.3.36. 1-((4-chlorophenyl)thio)-3-phenoxypropan-2-ol (5ga) Yellow oil; H NMR
(400 MHz, CDCl ) δ 7.32–7.20 (m, 6H), 6.99–6.93 (m, 1H), 6.89–6.83 (m, 2H),
1
2
2
2
2
91
92
93
94
3
11
15
[32]
1
2
2
2
2
2
95
96
97
98
99
3
4.14–3.98 (m, 3H), 3.21 (m, J = 13.9, 5.6 Hz, 1H), 3.11 (m, J = 13.9, 6.8 Hz, 1H),
2.59 (s, 1H). Anal. Calcd for C H ClO S: C, 61.11; H, 5.13. Found: C, 61.29; H,
15
15
2
5.38.
14

ACCEPTED MANUSCRIPT
[
32]
1
3
3
3
3
3
00
01
02
03
04
4.3.37. 1-phenoxy-3-(p-tolylthio)propan-2-ol (5gb) Yellow oil; H NMR (400 MHz,
CDCl ) δ 7.32–7.28 (m, 2H), 7.27–7.21 (m, 2H), 7.07 (d, J = 7.9 Hz, 2H), 6.97–6.91
(m, 1H), 6.87–6.83 (m, 2H), 4.13–3.95 (m, 3H), 3.18 (m, J = 13.8, 5.5 Hz, 1H), 3.08
(m, J = 13.8, 6.8 Hz, 1H), 2.69 (s, 1H), 2.28 (s, 3H). Anal. Calcd for C16H O S: C,
18 2
3
70.04; H, 6.61. Found: C, 69.86; H, 6.48.
3
3
05
06
References and Notes
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
07
08
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
[1] Ollevier, T.; Lavie-Compin. G. Tetrahedron Lett. 2004, 45, 49–52.
[2] Shimizu, M.; Yoshida, A.; Fujisava, T. Synlett 1992, 3, 204-206.
[3] Sreedhar, B.; Radhika, P.; Neelima, B.; Hebalkar, N. J. Mol. Catal. A: Chem.
2007, 272, 159-163.
[4] Mohammadpoor-Baltork, I.; Tangestaninejad, S.; Aliyan, H.; Mirkhani, V. Synth.
Commun. 2000, 30, 2365-2374.
[5] Iranpoor, N.; Salehi, P. Synthesis 1994, 11, 1152-1154.
[6] Moberg, C.; Rakos, L.; Tottie, L. Tetrahedron Lett. 1992, 33, 2191-2194.
[7] Bradley, D.; Williams, G. Org. Biomol. Chem. 2005, 3, 3269-3272.
[8] Posner, G. H.; Rogers, D. Z. J. Am. Chem. Soc. 1977, 99, 8208-8214.
[9] Procopio, A.; Costanzo, P.; Dalpozzo, R.; Maiuolo, L.; Nardi, M.; Oliverio, M.
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Supporting Information
An efficient catalyst for ring opening of epoxides with phenol
and thiophenol under solvent-free conditions
a,
a
a
a
a
Hong-fei Lu *, Jun-tao Zhou , He-long Cheng , Lei-lei Sun , Fei-fei Yang , Run-ze
a
a
b,
Wu , Yu-hua Gao , Zhi-bin Luo *
School of Biology and Chemical Engineering, Jiangsu University of Science and
Technology, Zhenjiang, China
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang,
China
a
b
1

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Experimental
. General information
All commercially available reagents were used without further purification.
1
Reaction progress was monitored with thin layer chromatography (TLC) performed
on GF254 silica gel plates. Column chromatography was performed with silica gel
1
2
00-300 mesh. All H NMR spectra were recorded in CDCl solution and reported in
3
ppm (δ). 1H NMR spectra were referenced internally to the residual proton resonance
in CDCl (δ=7.26 ppm), or with tetramethylsilane (TMS, δ=0.00 ppm) as the internal
standard.
3
2
. General procedure for the catalyst (C
4 12 2 2 6 2
H N ) [BiCl ]Cl·H O
Piperazine (10 mmol 0.86 g), BiCl (6.8 mmol, 2.15 g) and 35% aqueous HCl (3
3
mL) were mixed and dissolved in 30 mL of water, heated to 353 K to form a clear
solution. The reaction mixture was cooled slowly to room temperature, block crystals
of the title compound was collected after fifteen days.
3
. General procedure for ring opening of epoxides with phenol and thiophenol
A mixture of epoxide (1.1 mmol), phenol/thiophenol (1.0 mmol), and
(C H N ) [BiCl ]Cl·H O (0.01 mmol) was stirred in a flask. The course of the
4 12 2 2 6 2
reaction was monitored by TLC, complete disappearance of the raw materials was
observed within 10 min. The mixture was diluted by ethyl acetate (10 mL) and the
catalyst was separated from the organic phase by a simple filtration. The organic
3
phase was washed successively with aqueous NaHCO and water, dried over
anhydrous Na SO , and evaporated under reduced pressure to provide the crude
2
4
product, which was purified by column chromatography.
2

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Crystal data
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H NMR spectrum of compound 3aa
1
H NMR spectrum of compound 3ab
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H NMR spectrum of compound 3ac
1
H NMR spectrum of compound 3ad
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H NMR spectrum of compound 3ae
1
H NMR spectrum of compound 3ba
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H NMR spectrum of compound 3bb
1
H NMR spectrum of compound 3be
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H NMR spectrum of compound 3ca
1
H NMR spectrum of compound 3cd
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H NMR spectrum of compound 3ce
1
H NMR spectrum of compound 3da
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H NMR spectrum of compound 3db
1
H NMR spectrum of compound 3dc
11