Catalysis Communications 10 (2009) 557–560

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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Solvent-free ring opening reaction of epoxides using quaternary

ammonium salts as catalyst
Gabriella Fogassy, Catherine Pinel *, Georges Gelbard
Université de Lyon, CNRS, UMR 5256, IRCELYON, 2 Avenue Albert Einstein, F-69626 Villeurbanne, France

a r t i c l e i n f o a b s t r a c t

Article history: Ring opening reaction of 1,2-epoxydodecane to the corresponding diacetate diester is described. Quater-
Received 31 July 2008 nary ammonium salts were found to be excellent catalysts for the acetylation reaction of the epoxide
Received in revised form 27 October 2008 with acetic anhydride, where its activity was compared to different chloride salts. While in the presence
Accepted 28 October 2008
of chloride salts no reactions were observed without activation, excellent yields (up to 100%) were
Available online 12 November 2008
achieved in the presence of quaternary ammonium salts. The effect of heterogeneous catalysts was com-
pared to homogeneous ones.
Keywords:
Ó 2008 Elsevier B.V. All rights reserved.
1,2-Epoxydodecane
Acetylation
Quaternary ammonium salt
Diester

1. Introduction Previous studies reported that tetraalkylammonium salts

The ring opening reaction of oxiranes to the corresponding alco-
hols is a useful organic reaction [1] and the acetylation of alcohols is
a fundamental process for protecting hydroxyl groups [2]. Therefore,
the formation of diacetoxy compounds from direct opening of the
epoxide is interesting not only as building blocks, but also as syn-
thetic intermediates. Several activation agents were developed to
perform efficient oxirane ring opening to the corresponding diester.
Acetylation of epoxides with acetic anhydride in the presence of
various amine catalysts yielded the corresponding diacetoxy es-
ters. Shevets et al. reported the opening of ethylene oxide by
Ac2O in the presence of pyridine in 45–93% yields depending on
the reaction conditions [3]. Swindell et al. investigated acylation
of epoxycyclooctane in the presence of 1,8-diazabicyclo-[5.4.0]un-
dec-7-ene and LiCl in tetrahydrofuran which gave the vicinal diac-
etate in 70% yield [4].
Phosphine-catalyzed ring opening reaction of epoxides with
2 equiv of Ac2O in the presence of 10 mol% of Bu3P has been devel-
oped by Fan et al. with up to 98% yield [5].
The acid-catalyzed ring opening of epoxides in the presence of
Ac2O is well known. Evans et al. reported that 3,4-epoxy-1-butene
is converted to 3,4-diacetoxy-1-butene in 70% yield when hydro-
chloric acid was used as a catalyst, while only a 39% yield was ob-
tained in the presence of a catalytic amount of anhydrous zinc
chloride [6].
remarkably prompted the ring opening reactions of epoxides with
various nucleophiles. Studies by Yoshino et al. disclosed the ring
opening of 1,2-epoxycyclohexane in the presence of different tet-
raethylammonium halide [7]. The best result can be achieved with
the expensive iodide-based catalyst. Another group, Fraser–Reid et
al. extended this reaction to epoxypyranosides catalyzed by tetra-
butylammonium acetate to give the corresponding vicinal diace-
tates in 70% yield [8].
Most of these investigations were carried out in the presence of
solvent or the suggested methods are expensive and/or toxic but
no systematic research was done with different ionic salts in sol-
vent free conditions.
Herein we report an oxirane ring opening reaction with acetic
anhydride catalyzed by different quaternary ammonium salts. In
order to respect the green chemistry principles, we aimed to use
the most convenient safe catalyst. Ideally, the reaction should be
carried out in the absence of solvent and in equimolar ratio of each
reactant. As a model, the study was based on the acylation of 1,2-
epoxydodecane to the corresponding diester product in the pres-
ence of a large range of homogeneous catalysts. For comparison
inorganic salts were evaluated. The interest of recyclable heteroge-
neous catalyst will be investigated also.
2. Experimental
2.1. Materials

* Corresponding author. 1,2-Epoxydodecane was purchased from Aldrich. Acetic anhy-

E-mail address: catherine.pinel@ircelyon.univ-lyon1.fr (C. Pinel). dride, quaternary ammonium salts (tetrabutylammonium chloride

1566-7367/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2008.10.039
558 G. Fogassy et al. / Catalysis Communications 10 (2009) 557–560

(Bu4N+Cl), tetrabutylammonium bromide (Bu4N+Br), tetrabutyl-
ammonium acetate (Bu4N+AcO), tetramethylammonium chloride
(Me4N+Cl), tetrapentylammonium bromide ((C5H11)4N+Cl), ce-
tyl-trimethylammonium bromide (CH3(CH2)15N+Me3Cl), 1-butyl-
3-methyl-imidazolium chloride (BMIM+Cl), cetylpyridinium chlo-
ride (CH3(CH2)15Py+Cl)), chloride salts (KCl, CsCl, LiCl) and 18-
Crown-6 were Aldrich products, and used as received. Amberjet
4200 Cl (found: N 6%, Cl 13%) and Amberlyst A-26 Cl (found: N
5%, Cl 12%) resin were available from Rohm and Haas.
2.2. Pre-treatment of the ammonium resin
Amberjet 4200 Cl and Amberlyst A-26 Cl resins were pre-trea-
ted according to the following procedure: 10 ml wet resin was
washed with 30 ml 0.5 M HCl following by the water treatment till
pH 4–5 and finally washed successively with ethanol, methanol,
acetone and tetrahydrofuran. The residue was dried under vacuum
at 50 °C overnight.
2.3. General method for ring opening reaction of 1,2-epoxydodecane
The reaction was carried out in a 5 ml closed vial equipped with
a magnetic stirrer. A mixture of 1 mmol (0.2 g) of 1,2-epoxydode-
cane, 1 mmol (0.1 ml) acetic anhydride and 0.05 mmol catalyst
were introduced into the vial. The reaction mixture was heated
to the desired temperature under stirring. After cooling, the mix-
ture was treated with water and extracted with ether. The organic
layer was dried over MgSO4 and after evaporation of the solvent
the product was isolated as a colourless liquid.
The products were identified on the basis of their 1H and 13C
NMR (Bruker AV 250). Conversions and yields were determined
by gas chromatographic (60 m long DB-23 capillary column with
nitrogen as the carrier gas, FID). The conversion was based on
the epoxide transformation (1H NMR (CDCl3, 250 MHz) d ppm:
0.8 (t, 3H, H12), 1.19 (m, 16H, H4-10), 1.48 (m, 2H, H3), 1.97 (s, 6H,
H14,16), 3.95 (dd, 1H, H1), 4.13 (dd, 1H, H1), 4.97 (m, 1H, H2). 13C
NMR (CDCl3, MHz) d ppm: 13.9 (C12), 20.6 (C16), 20.9 (C14), 22.5
(C11), 25 (C4), 29 (C5-9), 30.5 (C3), 31.7 (C10), 65 (C1), 71.4 (C2),
170.4 (C15), 170.6 (C13) identical to reported data [11]).
3. Results and discussion
The catalytic reaction of oxirane ring opening with acetic anhy-
dride was investigated in the presence of different salts in order to
choose the best catalyst for acylation of 1,2-epoxydodecane
(Scheme 1) to the corresponding diacetate.
Several parameters were screened such as the temperature, the
amount of the acylating agent, the amount of catalyst, the nature of
the catalyst in order to evaluate their influence on the reaction.
In the presence of a slight excess of acetic anhydride (1.2 equiv),
the diacetate was formed exclusively. As expected, decrease of the
temperature, gave lower reaction rate: at 80 °C and 90 °C after 6 h,
the yield of diester reached 51% and 85%, respectively, while com-
plete conversion was reached at 100 °C [9]. Under similar condi-
tions, blank experiments were performed, in the absence of
ammonium salts, and no reaction were observed at any tempera-
ture. Thus we decided to work at 100 °C with the complete
conversion.
The reaction was carried out in the absence of solvent; there-
fore, it is of interest to minimize the excess of Ac2O used as reac-
tant. It turned out that the quantity of the anhydride (from 1 to
2 equiv) has only a slightly effect on the reaction rate. Learning
from this result it is ideal to work only with 1 mol equiv of anhy-
dride for further development of this methodology.
In the presence of 10 mol% catalyst, after 3 h reaction at 100 °C,
almost complete conversion of epoxydodecane was observed
(Fig. 1). GC–MS analyses showed that the main product was the ex-
pected 1,2-dodecanediol diacetate and a by product was formed up
to 7 mol%. This latter was attributed to the intermediate chloroace-
tate. Lowering the amount of catalyst not only decreased the con-

14 13 O
O Ac2O
12 O 15 16
catalyst 10 8 6 4 2
11 9 7 5 3 1
O
1 4
Scheme 1. Oxirane ring opening reaction with acetic anhydride.

97
100 87 100
90
80 82
58 80
60
(%)

57
60
40
(%)

26 Conversion 1
20 40
25 Yield 4
0 conv. 20
10
52 yield
2.5
amount of ca 14 0
talyst (m ol%)
0 2 4 6 8 10 12 14
t (h)

Fig. 1. (a) Influence of the Bu4N+Cl quantity on the epoxide conversion and on the diacetate yield. Reaction conditions: 1,2-epoxydodecane/Ac2O = 1/1, 3 h, 100 °C; (b)
Conversion of epoxide (1) and formation of diacetate (4) vs. time. Reaction conditions: 1,2-epoxydodecane/Ac2O = 1/1, 5 mol% Bu4N+Cl, 100 °C.
 G. Fogassy et al. / Catalysis Communications 10 (2009) 557–560 559

version but also the proportion of the chloroacetate intermediate.
Therefore, the catalyst loading can be reduced easily to 5 mol%.
However, longer time is required to complete the reaction (Fig. 1).
At 100 °C, the opening reaction occurred smoothly in the pres-
ence of 5 mol% Bu4N+Cl and 1 mol equiv acetic anhydride. After
12 h reaction, the conversion was complete and only the expected
diester was obtained.
Previously, it was reported that the tetraethylammonium halide
salts served as nucleophile to attack the oxirane to form a halide
salt [7]. To support this information we run a reaction with a stoi-
chiometric amount of tetrabutylammonium chloride (Fig. 2).
During the heating of the reaction from room temperature to
100 °C, the epoxide was already largely converted due to the pres-
ence of an equimolar amount of ammonium salts. In that case, we
noticed that the chloroacetate intermediate 4 is the main product,
which is further, transformed slowly to the desired product 3.
Based on the above experience and according to previous liter-
ature data, a plausible mechanism was proposed for catalysed
epoxide ring opening with Ac2O (Scheme 2).
In the initial step, the active halide opened via nucleophilic at-
tack the epoxide 1 to yield the chloroalcolate 2 (not detected) that
reacted with the acetic anhydride to produce the observed chloro-
acetate 3. The final step is the direct displacement of the halogen-
substitute by acetate ion to give the ring opening product with
regeneration of the Bu4N+Cl. Only one isomer of the chloroacetate
was formed due to the different reactivity of both positions.
100
80
60 Yield 4
(%)
This transformation has been applied to several anhydrides
yielding a range of 1,2-substituted diesters (Table 1, entries 5–7).
On the other hand, different epoxides were evaluated. Terminal
epoxystyrene and disubstituted cis cyclohexane epoxide react effi-
ciently with acetic anhydride (entries 3 and 2). However, after 24 h
reaction, only moderate conversion of trans-disubstituted epoxides
was achieved (entry 4).
In previous studies [7] it was reported that 1,2-epoxycyclohex-
ane was successfully opened to the corresponding trans diacetate
in the presence of the expensive tetraethylammonium iodide cata-
lysts at 130 °C, the bromide and the chloride corresponding ammo-
nium salts being less active. Based upon these results, we
envisioned to perform the ring opening reaction of the 1,2-epoxyd-
odecane with different chloride and bromide quaternary ammo-
nium salts (Table 2).
The quaternary ammonium halide catalyst is the critical actor in
this reaction. The influence of the nature of the catalyst is reported
in Table 2 and the screening of the anion and cation moieties was
studied.
First chloride, bromide and acetate tetrabutylammonium salts
were compared (entries 1–3). Good to excellent yield was achieved
whatever the counter-anion. Considering the mechanism, it can be
assumed that tetraalkylammonium acetate is formed during the
catalytic cycle that could explain the similar activity observed with
these different anions. Considering the cost of this different quater-
nary ammonium salts, the chloride is the best one.
Under identical reaction conditions the tetramethylammonium
chloride is much less effective (entry 4). On the other hand, more
lipophilic ammonium salts exhibited similar reactivity (entries 5
and 6). The nature of the nitrogen moiety was also studied. Ionic
liquid (1-butyl-3-methyl-imidazolium chloride, entry 7) was
investigated in this reaction and displayed a slightly lower activity.
Pyridinium based salts (entry 8) were also active in this reaction.

Table 1
Conv 1
40 Ring opening with different anhydride.

Entry R, R0 Anhydride Conv. (%)

20 1 C10H21, H Ac2O 87
2 (C2H5CO)2O 85
0 3 (C3H7CO)2O 85
0 5 10 15 20 25 30 4 (C4H9CO)2O 86

t (min) 5 Ac2O 93
6 Ph, H 83
Fig. 2. Product distribution as a function of time with 1 mol equiv of reactants. 7 trans-Ph, Ph* 40
Reaction conditions: 1 mol equiv 1,2-epoxydodecane, 1 mol equiv Ac2O, 1 mol
Reaction conditions: epoxide/anhydride = 1/1, 5 mol% Bu4N + Cl, 3 h; *24 h.
equiv Bu4N+Cl, 100 °C.

O O

O
O R4N+X- 1

4 O

O
X X
3 2 O- N+R4

O
CH3CO2- N+R4 H3COC COCH3

Scheme 2. Catalytic ring opening mechanism in the presence of ammonium acetate.

560 G. Fogassy et al. / Catalysis Communications 10 (2009) 557–560

Table 2 available. In this study, Amberlyst A-26 and Amberjet 4200 resins
Influence of the catalyst type on the acylation. were evaluated. Both are polystyrene-based supports, the former
Entry Catalyst Conversion (%) Yield (%) being a macroporous polymer while the latter one is a gel-type
1 +
Bu4N Cl 
87 82 polymer (Table 2, entries 10 and 11).
2 Bu4N+Br 82 76 The gel-type polymers contain less than 8% crosslinking agent
3 Bu4N+AcO 81 80 and are able to swell in suitable solvent. On the other hand, the
4 Me4N+Cl 32 32 macroporous polymers do not swell and the active groups are at
5 (C5H11)4N+Br 69 68
6 CH3(CH2)15N+Me3Cl 69 60
the surface. Both polymers disclosed dramatic lower activity in
7 BMIM+Cl 60 56 comparison to the corresponding homogeneous catalyst. After 6 h
8 CH3(CH2)15Py+Cl 77 74 reaction time, less than 10% of epoxide was converted in the pres-
9 Amberlyst A-26* 10 8 ence of 5% catalyst based on the ammonium amount (Table 2).
10 Amberjet 4200* 4 3
Considering these low conversions, we performed the reaction
Reaction conditions: 1,2-epoxydodecane/Ac2O = 1/1, 5 mol% catalyst, 100 °C, 3 h; with 20 mol% of heterogeneous catalyst and we studied the recy-
*
6 h. clable character of the ammonium resin. The Amberlyst resin
was recovered after the reaction by simply washing with an organ-
ic solvent (ether) and after with subsequent drying in vacuum. The
Table 3 dry catalyst was used again in the next reaction without further
Influence of different Cl salts on acylation. regeneration and was recovered after each reaction accordingly.
The results obtained in the series of reactions are illustrated in
Entry Catalyst Quantity (mol) Conversion (%) Yield (%)
Fig. 3.
1 LiCl 0.2 0 –
Nevertheless of the low activity of the heterogeneous catalyst
2 CsCl 0.2 0 –
3 KCl 0.2 0 – no significant deactivation was observed, even after the fourth
4 KCl/C18 crown 0.2/0.2 63 58 use. In order to get higher conversions, the reaction was main-
5 AcOK 0.2 0 – tained for 48 h (Fig. 3). In that case, we observed a small decrease
6 AcOK/C18 crown 0.2/0.2 100 100 of the conversion after five cycles (75% vs. 85% yield) that could be
Reaction conditions: 1,2-epoxydodecane/Ac2O = 1/1, 100 °C, 3 h. attributed to a partial degradation of the polymer at these
temperatures.

4. Conclusion
100
3h 48h
The application of different quaternary ammonium salts as an
80 effective catalyst has been illustrated by its use in oxirane ring
opening reaction with acetic anhydride. The acetylation of 1,2-
epoxydodecane took place in good to excellent yield in a catalytic
Yield (%)

60
reaction. One of the significant features is that only 1 mol equiv
acylating agent enough to obtain the corresponding diacetate
40
exclusively. It should be pointed out that there is no need the addi-
tion of solvent, therefore, we can work in so called solvent free con-
20 dition. Among the studied catalysts, tetrabutylammonium chloride
and acetate are the best ones. The tested polystyrene resins can be
0 recovered and recycled. This reaction was applied to several anhy-
1 run 2 run 3 run 4 run 5 run dride and epoxide and further works are under progress to extend
Fig. 3. Effect of catalyst reuse on the product yield in the Amberlyst catalyzed this reaction to epoxidized fatty acid esters.
acylation of 1,2-epoxydodecane. Reaction conditions: 1,2-epoxydodecane/Ac2O = 1/
1, 0.2 mol equiv Amberlyst, 100 °C. Acknowledgments

We thank Agrice-ADEME (Grant no. 2005-11) and TESF for

We extended our study to evaluate the role of inorganic salts in
the ring opening reaction. Varieties of chloride ion salts were stud-
ied for this reaction the results are collected in Table 3.
As expected, whatever the cation these non-activated salts were
not efficient in the acylation reactions even with 20 mol% ratio (en-
tries 1–3). 18-Crown-6-ether was added to the KCl salts. As it is
well known, crown ethers chelate cations [10] such as potassium,
increasing the nucleophilic activity of the counter-anion Cl. As a
result the reaction occurred, yielding the diester with 58% yield
after 3 h reaction (entry 4). The same results were achieved with
the potassium acetate that was active only in the presence of 18-
crown-6-ether (entry 6).
The use of polymer-supported catalyst allows the easy separa-
tion from the reaction mixture to the potential reuse of the resins.
Some supported quaternary ammonium salts are commercially
financial supports (GF).
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