A Strategy for the Simultaneous Synthesis of Methallyl Alcohol and Diethyl Acetal with Sn-Β

Article abstract of DOI:10.1002/cssc.201701435

A new strategy was developed to simultaneously produce two important chemicals, namely, methallyl alcohol (Mol) and diethyl acetal (Dal) from methacrolein in ethanol solvent at low temperature with the use of Beta zeolites modified by tin (Sn-β catalysts). All the Sn-β catalysts were prepared by the solid-state ion-exchange method, wherein the calcination step was conducted under different gas atmospheres. The catalyst precalcined in Ar (Sn-β-Ar) had a reduced number of extra-framework Sn species and enabled more Sn species to be exchanged into the framework as isolated tetrahedral Sn^IV, enhancing the catalytic activity of the Meerwein–Ponndorf–Verley (MPV) reaction. The sodium-exchanged Sn-β-Ar, with a reduced number of weak Br?nsted acid sites, led to an even better selectivity for Mol, owing to the restriction of the side reactions such as acetalization, addition, and etherification. Under optimized catalyst and reaction conditions, the yield of Mol and Dal reached approximately 90 % and 96 %, respectively. The possible reaction pathways, along with a complex network of side products, was proposed after a detailed investigation through the use of different substrates as reactants. The fine-tuning of Sn-β catalysts through different treatments discussed in this work is of great significance toward the understanding and manipulation of complex reactions between α,β-unsaturated aldehydes and primary alcohols.

Full text of DOI:10.1002/cssc.201701435

Accepted Article
Title: A Strategy for Simultaneous Synthesis of Methallyl Alcohol and
Diethyl Acetal with Sn-β
Authors: Wenda Hu, Yan Wan, Lili Zhu, Xiaojie Cheng, Shaolong Wan,
Jingdong Lin, and Yong Wang
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ChemSusChem
10.1002/cssc.201701435
FULL PAPER
A Strategy for Simultaneous Synthesis of Methallyl Alcohol and
Diethyl Acetal with Sn-β
Wenda Hu, Yan Wan, Lili Zhu, Xiaojie Cheng, Shaolong Wan*[a, b, c] Jingdong Lin,[a, b] and Yong
[
a]
[a]
[a]
[a]
Wang [a, b, c, d]
Abstract: Herein we report a strategy to simultaneously produce two
important chemicals namely methallyl alcohol (Mol) and diethyl
acetal (Dal) from methacrolein (Mal) in ethanol solvent at low
temperature with the use of Beta zeolites modified by tin (Sn-β
catalysts). All Sn-β catalysts were prepared by the solid-state ion-
exchange (SSIE) method, wherein the calcination step was
conducted in different gas atmospheres. The one pre-calcined in Ar
synthesis strategy of Mol through hydrogenation of
methacrolein (Mal) was reported in a Japanese patent
JP2000290546, where homogeneous Ru-based catalysts
were applied. Alternatively, Shimasaki et al. proposed vapor
phase hydrogen transfer between Mal and ethanol,
catalyzed by a less expensive and heterogeneous catalyst,
[3a, 3b]
i.e. modified MgO.
However, the process suffered a
(Sn-β-Ar) diminishes the number of extra-framework Sn species and
low conversion of Mal even under high temperature, and
the catalyst stability is also an issue as well, especially with
moisture existence. Therefore, the development of an
effective but environmentally benign tactic for Mol synthesis
is still needed.
instead enables more Sn species exchanged into the framework as
isolated tetrahedral Sn (IV), thus enhancing the catalytic activity of
Meerwein-Ponndorf-Verley (MPV) reaction. The sodium-exchanged
Sn-β-Ar, with the weak Brønsted acid site further diminished, leads
to an even better result to Mol, thanks to the restriction of those side
reactions such as acetalization, addition and etherification. Under
optimized catalyst and reaction condition, the yield of Mol and Dal
could reach about 90% and 96%, respectively. The possible reaction
pathway, along with the complex network of side products, was
proposed after a detailed investigation through the use of different
substrates as the reactants. The findings of Sn-β fine-tuned through
different treatment in this work, are of great significance toward
understanding and manipulating the complex reaction between ɑ, β-
unsaturated aldehydes and primary alcohols.
The direct hydrogenation of ɑ, β-unsaturated aldehydes like
methacrolein (Mal), readily obtained by selective oxidation
[
4]
of isobutene, requires selective activation of the carbonyl
bond while retaining the active C-C double bond intact. This
is difficult to achieve with the more typical approaches
based on the use of noble metal catalysts. Alternatively, the
Meerwein-Ponndorf-Verley (MPV) reduction, namely the
hydrogen transfer reaction between alcohol and aldehyde,
has long functioned as a tool for selectively reducing ɑ, β-
unsaturated aldehydes to ɑ, β-unsaturated alcohols (like
Mol), while not reducing the double carbon bond.[
5a, 5b, 5c]
Introduction
Homogeneous MPV catalysts, such as aluminum alkoxides,
[
1]
are traditionally used to convert aldehyde. Replacement
by heterogeneous catalysts is therefore of interest. A
variety of solid MPV catalysts have been reported, and
Methallyl alcohol (Mol) is an important chemical, widely
used as a raw material in making various polymers,
pharmaceuticals, pesticides and other allyllic compounds.
Mol can be the precursor of 2-methyl-1,4-butanediol, which
plays important parts in the pharmaceutical industry and in
[
7]
successfully applied: metal oxides,
alkoxides, and zeolites.
grafted metal
[
8]
[9a, 9b]
Among them, Sn-β has
shown very good activity and selectivity for MPV reductions,
[
1]
[9a,
polyester
chemistry.
Also,
2-methylglycidol,
the
acting as a strong and water-tolerant Lewis acid catalyst.
1
0a, 10b]
epoxidation product of Mol, functions as feedstock for
synthesis of biologically active compounds, cosmetics, and
The well-known examples include isomerization of
[
11]
glucose to fructose,
derivatives,
selective synthesis of lactic acid
and chemoselectively catalyze Baeyer-
[
2a, 2b]
[12]
immunomodulators for therapy of diseases.
The
[
13]
conventional method to prepare Mol is hydrolysis of
methylallyl chloride, which would have to employ alkali,
organic solvent, as well as high temperature and pressure.
To avoid the use of such harsh environment, a few efforts
of novel replacement have been found in the literature. A
Villiger oxidation of ketones to lactones,
etc.. Therefore,
Sn-β is also expected as a promising catalyst for selectively
synthesis of ɑ, β-unsaturated alcohols (Mol) through MPV
reaction in this work.
Besides the catalyst, the choice of alcohols is also a key
consideration for practical application. Secondary alcohols
such as 2-propanol are more often chosen as hydrogen
[
a]
W. Hu, Y. Wan, L. Zhu, X. Cheng, S. Wan, J. Lin, and Y. Wang
College of Chemistry and Chemical Engineering
Xiamen University
Xiamen 361005, China
E-mail: swan@xmu.edu.cn; Wang42@xmu.edu.cn.
S. Wan, J. Lin, and Y. Wang
Collaborative Innovation Center of Chemistry for Energy Materials
Xiamen 361005, China
S. Wan, and Y. Wang
National Engineering Laboratory for Green Chemical Productions
of Alcohols-Ethers-Esters
Xiamen 361005, China
[
7, 9a, 10a]
donors and solvents for MPV reactions,
due to their
evidently lower reduction potential and less complexity of
the product distribution compared with that of primary
[
b]
c]
[14]
alcohols.
However, primary alcohols, especially ethanol,
have a lot of advantages in practical application. First, it is
industrially available in large scales by a well-developed
process. Moreover, the MPV product from ethanol leads to
acetaldehyde, which is of higher market value than the
alcohols. The direct oxidation of ethanol to aldehyde is very
challenging to control, since it tends to be fully oxidized to
acetic acid. With ethanol as the solvent, acetaldehyde will
be further reacted and exist in its acetal form, namely
diethyl acetal (Dal), which can be readily converted back to
the aldehyde. An alternative is just keeping Dal as the
desired product. Dal is also an important chemical, widely
used as oxygenated additive for diesel fuel to reduce the
[
[c]
Y. Wang
Voiland School of Chemical Engineering and Bioengineering
Washington State University
Pullman, WA 99164 , United States.
Supporting information for this article is given via a link at the end
of the document.
This article is protected by copyright. All rights reserved.

ChemSusChem
10.1002/cssc.201701435
FULL PAPER
emission of particles and NO
some pharmaceuticals and perfumes.
X
, and the precursor to prepare
not very clear about the exact mechanism or specific active
site of the catalyst. Along with this line, the evaluation of the
reaction network involved in our work could shed further
light on the insight of the reaction mechanism over Sn-β
catalysts.
[
15]
Dal production is
generally realized by reaction of acetaldehyde and ethanol
in acid solution, or through the use of ion-exchange resins
and zeolites.[
16a,
16b]
However, the direct use of
acetaldehyde suffers from its low boiling point (294 K),
toxicity and instability. Liu et al. then developed a more
complicated two-step process for the synthesis, including
initial oxidation of ethanol and subsequent acetalization of
Herein, we first report a facile strategy to simultaneously
synthesize Mol and Dal (or acetaldehyde) in a high yield at
low temperature with SSIE post-synthesized Sn-β. The
reaction conditions were optimized, and a complex reaction
pathway will be revealed in detail. Furthermore, we
systematically investigated a series of catalysts prepared by
different pre-treatment measures, the structure and acid
property of which were all thoroughly characterized. The
correlation of catalyst properties with reaction selectivity
and activity is especially emphasized.
[
17]
formed acetaldehyde with bifunctional catalysts.
yield reached 70.5% after removal of water with the aid of
A zeolites, the highest so far reported in the open
The
3
literature. Relevant to this, the current approach shows
advantages. As shown in Scheme 1, this route is expected
not only to readily produce more valuable products, namely
Mol and Dal (or acetaldehyde), but more importantly with
high product yield and process efficiency.
The Sn-β catalyst is tedious and time-consuming to prepare
[
9a]
using conventional hydrothermal synthesis routes.
The
post-synthesis of Sn-β has been described as an efficient
replacement, using a variety of ways to introduce Sn
species into the zeolite framework. Li et al. reported a solid-
gas reaction of dealuminated beta zeolite with SnCl
4
vapor
at elevated temperatures to obtain the Sn-β catalyst with a
[
18]
varied loadings of Sn.
Dijkmans’s group successfully
·5H O in dry
The solid-state
prepared 1.6 wt% Sn-β via grafting with SnCl
isopropanol under reflux condition.
4
2
[
19a, 19b]
ion-exchange (SSIE) method, as proposed by Hermans et
al., has attracted a lot of attention due to its many
advantages. For example, H-β zeolite can be directly used
as the starting material. The long synthesis times required
in the traditional method are no longer needed, and the
small crystallite sizes can be maintained as well, which
Scheme 1. MPV reduction and tandem acid acetalization of acetaldehyde.
could be critical for reducing diffusional resistances during Results
the reaction.[20a, 20b] The method also shows flexibility in
tuning the number and the environment of Lewis acid sties
as well as the amount of medium/weak Brønsted acid
Catalyst characterization
counterpart of the catalyst by simply changing the pre-
treating conditions. Recently, Hermans and Hammond et al.
reported a modified post synthesis SSIE method,
[
21a, 21b]
The topology of beta zeolite was retained intact for the
prepared deAl-β, Sn-β Sn-β-Ar and Sn-β-Ar-Na, as
confirmed from the XRD results in Figure 1. This indicates
no destruction of zeolite framework occurred through the
acid treatment, incorporation of Sn and calcination in air or
which was pre-heated in inert gas instead of flowing air.
The modified method was claimed to help diminish extra-
framework Sn species and generate more isolated
tetrahedral Sn(IV), leading to increased Lewis acid at the
cost of diminished moderate/weak Brønsted acid sites.
[
20a, 20b, 21a]
argon, consistent with earlier reports.
amount of SnO does exist in Sn-β, evidenced by
occurrence of the reflection peaks at 26.6 , 33.9 , and 51.8
A small
2
°
°
°
It is known that there are also weak Brønsted sites (net
silanol groups) and some extra-framework Sn species
besides the framework isolated tetrahedral Sn(IV) sites,
，
SnO
ascribed to the (110), (101) and (211) planes of rutile-like
[
24]
2
.
However, very weak peaks were found in those
[
18]
especially in the post-syntheis Sn-β zeolite.
Each of
three reflections for Sn-β-Ar and Sn-β-Ar-Na, suggesting
little existence of such extra-framework SnO
.
these active sites could catalyze different reactions
independently or in a concerted way, especially in the
cases where many or all possible reactions may occur. The
coexistence of various Brønsted and Lewis acid sites could
lead to a variety of reactions and a complex network.
Therefore it appears to be critical to control the relative
amounts of the different acid sites, the determining factor
for selectivity of the desired products. Indeed, recent
reports show that the catalysts can not only catalyze the
MPV reaction, but also play an important role in several
other reactions. Roman-Leshkov et al. hypothesized that
the acid–base characteristics of the hydroxyl groups of the
Sn-β are associated with the etherification steps, as well as
2
[
22]
the acetalization side reaction.
The acetalization is
actually quite common in alcohol solvent on Sn-β catalyst,
[
19a]
[23]
as observed by Sels et al.
Later Roman-Leshkov et al.
also reported that Sn-β can catalyze the carbon carbon
coupling between carbohydrates and formaldehyde. It is still
Figure 1. Powder XRD patterns of different Beta zeolites.
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ChemSusChem
10.1002/cssc.201701435
FULL PAPER
The physicochemical properties of the catalysts evaluated
in this work are summarized in Table 1. Both the
dealuminated and Sn-grafted zeolites exhibit BET surface
areas and micropore volumes similar to parent H-Beta,
again suggesting no significant structure damage during the
treatment, and in line with the previous XRD results. The
slightly increased specific surface area of deAl-β is probably
due to the removal of framework Al and consequent
[
18]
appearance of silanol nests.
The molar ratio of Si/Al
increased from 12.5 of initial zeolite to 833 after
dealumination, indicating that most Al was removed from
the zeolite structure. The molar ratios of Si/Sn are identical
2
for Sn-β and Sn-β-Ar, and the extra-framework SnO /deAl-β
also has a close range of Si/Sn ratio to ensure a
comparable Sn content. The SEM pictures in Figure S1
show that the average crystallite sizes of both Sn-β and Sn-
β-Ar (60- 80 nm) are much smaller than the reported
conventional synthesized Sn-β, with approximately 1000
Figure 2. FT-IR spectra of H-β, deAl-β, Sn-β and Sn-β-Ar.
[
18, 25]
nm crystallite diameter.
The coordination state of Sn can be identified by diffuse
reflectance ultraviolet visible (UV-vis) spectra, as seen in
Figure 3. The deAl-β, recorded as the bottom line, features
fairly low absorption, suggesting little electronic transition
occurring. The Sn-β detects a peak centered at 202 nm, as
well as a shoulder at higher wavelength. The former is
Table 1. Physicochemical properties of catalysts.
[
a]
[b]
-1
S
BET
2
V
micro
3
Molar
ratio[
Entry
Catalyst
Treatment
c]
-1
2-
[
m g ]
[cm g ]
assigned to the ligand-to-metal charge transfer from O to
4
+
Sn , which is characteristic of isolated tetrahedrally
1
2
3
H-β
deAl-β
Sn-β
-
460
0.20
Si/Al 12.5
Si/Al~833
Si/Sn~18
coordinated Sn in the framework of deAl-β; while the latter
is typically caused by the formation of extra-framework
H+
[20b, 28a, 28b, 28c]
498
0.21
SnO
2
species.
However, the Sn-β-Ar shows a
much more intense peak at 202 nm, but merely no
absorption at higher wavelength. This indicates that
framework Sn species are dominant in Ar-preheated Sn-β,
with much less extra-framework SnO2 compared with air-
treated counterpart, consistent with the XRD results
+
H &SSIE
467
0.18
+
H &SSIE&
4
5
6
Sn-β-Ar
437
489
410
0.17
0.17
0.17
Si/Sn~18
Ar
aforementioned. On the contrary, pure SnO
2
presents
+
Si/Sn~18
Si/Na~69
Sn-β-Ar-
Na
H &SSIE&
Ar&Na
significantly broad absorption from the about 200 nm to 300
[29]
nm, centering at 250 nm,
since the coordination state is
totally different from the framework Sn of beta zeolite. And
the framework Sn is also detected by Raman spectroscopy,
as displayed in Figure S2.
SnO
2
/de
H+&mixing
Si/Sn~11
Al-β
[
a] Specific surface areas obtained by BET method. [b] Calculated from t-plot.
[c] Determined by EDS.
The FT-IR spectra of H-β, deAl-β, Sn-β, and Sn-β-Ar are
shown in Figure 2. The parent H-β zeolite demonstrates
-
1
nearly no absorption at 950 cm , which is typically assigned
to Si–O stretching vibrations of Si–OH groups occurring at
[
26a, 26b]
structure defects.
The peak intensity is remarkably
enhanced for deAl-β, attributed from the formation of silanol
nests at the vacant sites after acid treatment. The near
disappearance again of this peak in Sn-β and Sn-β-Ar
suggested that the introduction of Sn has been successfully
incorporated into the dealuminated framework, forming the
tetrahedral Sn and thus turning off the nests of silanol due to
the incorporation of Sn into those defect framework sites. In
addition, the Sn-β and Sn-β-Ar present increased
2
Figure 3. UV-Vis spectra of deAl-β, Sn-β, Sn-β-Ar and SnO .
The acid properties of catalysts were characterized by FT-
IR with pyridine adsorption (Figure 4). The H-β possesses
both Brønsted and Lewis acid sites, characterized by the
-
1
absorbance intensity at approximate 575 cm , probably
owing to the enhanced framework vibration through the Sn
-
1
-1
[18, 28c, 30a, 30b]
incorporation.[
26a, 27]
band at 1540 cm and 1450 cm respectively.
The near disappearance of those bands in the
dealuminated zeolite suggests that most of both acid sites
-
1
were removed after acid treatment. The peaks at 1446 cm
-
1
and 1594 cm , vibrations of stretching modes of hydrogen-
bonded pyridine corresponding to hydroxyl groups of
[
31a, 31b, 31c]
zeolites,
are significantly enhanced probably due
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ChemSusChem
10.1002/cssc.201701435
FULL PAPER
to the formation of silanol nests. The subsequent
incorporation of Sn greatly enhances the Lewis acidity in
Sn-β, Sn-β-Ar and Sn-β-Ar-Na, as confirmed by the strong
reach nearly stable to 20% as the increase of Mal
conversion. There are also some minor products detected,
including the C etherification product and isobutanol (Ibol)
6
probably derived from Mol. More details about these
byproducts will be discussed in discussion section
Reaction conditions such as temperature, substrate
concentration, and catalyst loading also affect the
selectivities and the yields to Mol, Dal, and other side
products (Figure S3-4 and Table S1-3).
-
1
adsorption at 1611, 1490 and 1450 cm . Those are typical
vibration modes of the pyridine-rings adsorbed on the
[
31c, 32]
isolated tetrahedral Sn (IV) species in the beta zeolite.
The vibrations of hydrogen-bonded pyridine are decreased
a bit, when comparing Sn-β with Sn-β-Ar, indicating that
more silanol nests are occupied. The type of peak of Sn-β-
Ar-Na is identical to Sn-β-Ar, but the peaks corresponding
to hydroxyl groups at 1446 and 1594 cm- are lowered
significantly due to the presence of sodium ions. This
phenomenon indicates that the protons of the silanols are
successfully replaced with sodium, thus resulting in a
weakened Brønsted acidity, as will be discussed in the
1
3
catalytic activity section. Combining NH -TPD and FT-IR
with pyridine adsorption, the acid concentrations were
provided in Table S4.
Figure 5. Catalytic activity of Sn-β with time-on-stream. Optimized
reaction conditions: reflux, 350 K, 0.9 mmol Mal, 80 mmol ethanol and
0
.5 g Sn-β.
Catalytic activities with Sn-β-Ar
Compared to the results above, Sn-β-Ar catalyst exhibits a
superior catalytic activity toward the desired products under
the same optimized reaction conditions, as illustrated in
Figure 6. The yields of Mol and Dal rapidly rise to 81% and
Figure 4. FT-IR spectra of H-β, deAl-β, Sn-β, Sn-β-Ar and Sn-β-Ar-Na
with pyridine adsorption at 373 K and evacuation at 423 K.
93% respectively at 1 h on time stream, and the C8+
acetalization product is now cut into 4.5% from 14% in
Figure 5 of Sn-β. With the subsequent consumption of the
Catalytic activities of Sn-β
C
8+ side product, the released Mal will be further reacted to
form Mol, which then reaches up to 85% yield in 2 h. The C
6
Sn-β catalyst was studied over a wide range of reaction
conditions (such as temperature, substrate concentration,
types of alcohols used for MPV, and catalyst loading) to
optimized the yield of Mol. As shown in Figure 5, under the
optimized conditions over Sn-β, Mol is the primary product
from Mal, derived from MPV reduction with ethanol. Dal
from the acetalization of the aldehyde with ethanol is
another major product. The yields of Mol and Dal reach
about 71% and 94% respectively in 2 h, and then slightly
decrease due to secondary reactions. No acetaldehyde was
detected, which should be primarily produced from ethanol
through the MPV reaction, prior to the conversion to its
acetal form. This appears to suggest that the MPV reaction
is the rate-limiting step in Dal production, while the
subsequent acetalization step is not kinetically relevant.
addition product is also decreased to 15%, compared to
20% in Sn-β. The overall mass balance based on Mal is
well closed over the entire time-on-stream examined, which
mainly consists of MPV product Mol, C8+ acetal and C
addition product before 2 h.
6
The major byproducts are C8+ and C
6
species, mainly
resulting from the acetalization and addition-derived product
of Mal respectively. The former one shows a typical feature
of intermediate product, with the yield first reaching the
highest in 1 h and then continuously dropping to nearly
disappearance. This suggests that there is an equilibrium
between acetal product and Mal. As Mal is continuously
converted to Mol, Mal is depleted but replenished via the
Figure 6. Catalytic activity of Sn-β-Ar with time-on-stream. Optimized
reaction conditions: reflux, 350 K, 0.9 mmol Mal, 80 mmol ethanol and
0
.5 g Sn-β-Ar.
decomposition of acetal product. However, the yield of C
6
addition products follow the characteristic curve of stable
primary products, which increase monotonously and then
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ChemSusChem
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FULL PAPER
The drop in Dal yield is quite striking after 2 h. To shed light
on the mechanism of this phenomenon, the test was
intentionally extended to a long period of 8 h to exaggerate
the effect. As shown in Figure 6, the yield of Dal is further
declined to 87% after 8 h. The significant disappearance of
Dal is probably due to the evaporation of acetaldehyde, due
to its low boiling point about 294 K. Since it is much below
the reflux temperature 350 K, the condenser used in the
work is probably not capable to completely condense
acetaldehyde vapor back into the flask. Therefore, Dal
would remain relatively stable in less than 4 h, staying
under equilibrium with acetaldehyde (though under
detected level). However, if holding on the reaction long
enough, the slow but continual evaporation and loss of
acetaldehyde would shift the equilibrium and eventually
consume all the Dal, as seen in Figure S3b. With the
prolonged reaction time, two minor secondary products, i.e.
Discussion
Results from different catalysts
A variety of catalysts have been tested under the optimized
conditions described above in order to fully understand the
reaction network and the relationship and role of specific
acid sites. As shown in entry 1 of Table 3, there was no
activity in the blank run, where only reactants but no
catalysts were loaded. H-β catalyst can achieve nearly 30%
conversion, resulting in mostly the C8+ acetalization product
of Mal, but no MPV products were detected. The
dealuminated counterpart, deAl-β shows a diminished
activity, leading to about 24% conversions and the same
C
8+ acetal species as dominant products. It is generally
6
the C etherification product and Ibol also gradually build
up, which appears to be consistent with the slight decrease
in Mol yield.
believed that the Brønsted acid sites can effectively
catalyze the acetalization reaction.
Figure 4, there are both Brønsted and Lewis acid sites in H-
[34]
As evidenced in
β. The former are mainly ascribed to the framework Al
Catalytic activities with Sn-β-Ar-Na
(generating strong Brønsted acidity), while the latter more
related with partially coordinated Al atoms and extra-
[
35]
framework Al.
This clearly suggests that the relative
The Na-exchanged Sn-β-Ar zeolite further improved the
performance over the un-exchanged counterpart, which
was also applied in improving the selectivity of lactic acid
produced by sugar. As exhibited in Figure 7a, the yield of
Mol and Dal products now reach 90% and 96%,
respectively, in 3 h. The level of intermediate C8+ acetal
remains at a low level in 1 h, followed by nearly complete
disappearance after 2 h time-on-stream. The striking effect
is the depression of the side reactions over the Na-
strong Brønsted sites in H-β can effectively catalyze the
acetalization of Mal with ethanol, while the Lewis acid sites
present in H-β lack the ability to activate the MPV reaction.
The removal of the framework Al in deAl-β eliminates those
strong Brønsted acid sites, but moderate or weak Brønsted
acidity ascribed to the surface or the nest hydroxyl groups
are still present, as shown in FTIR spectra of Figure 2 and
Figure 4. These acid sites are active enough to produce an
acetalization product of Mal, but to a less extent.
[
33]
exchanged zeolite. The C
reduced to 10% over the 4 hours’ reaction, and there is
barely ether product and Ibol detected. The
enhancement of the desired Mol product and the inhibition
of C addition byproduct can be clearly seen in the direct
6
addition product is notably
C
6
The subsequent introduction of Sn into the framework forms
[
9a, 36]
strong Lewis acid sites,
accompanied with the
decrease of nest hydroxyl groups (moderate or weak
Brønsted acid sites). As a result, Mol and Dal are shown as
the major products, while the selectivity toward acetalization
of Mal was suppressed to a low level instead. The reason
why Dal yield, also derived from acetalization, was not
depressed will be discussed later. Another side product
from addition to the double C-C bond also occurs to a
notable level. We suggest that tetrahedral Sn Lewis acid
6
comparisons over the three Sn-β catalysts, as exhibited in
Figure 7b.
1
0
0
.0
.8
.6
Conversion
Mol
1.0
0.8
0.6
0.4
0.2
0.0
Dal
a
b
sites in Sn-β framework are responsible for the MPV
Mol
[23, 37]
reaction, rather than the extra-framework SnO
2
.
To
further prove this argument, extra-framework SnO
2
/deAl-β
was synthesized and employed under the same reaction
condition. As seen in entry 5, the conversion is comparable
to that of deAl-β, resulting in no Mol but only acetalization
0.4
0.2
C8+ acetal
C6 addition
C addition
6
2
products. When ‘pure’ SnO served as catalyst, there was
0.0
no reaction. This demonstrates that extra-framework Sn is
not catalytically active in the MPV, or the addition
0
1
2
3
4
air Ar Ar-Na
air Ar Ar-Na
Time / h
[
21a]
reaction.
Enhanced performance is achieved with the
employment of Sn-β-Ar, as shown in entry 8 of Table 3 and
Figure 7b. The superior performance may be the result of
the pre-heating step wherein the Ar might increase the
dispersion between Sn precursor and the dealuminated
zeolite, so that more Sn react with the silanol nests and
embed into the framework, resulting in a greater Lewis
acidity (as demonstrated in Figure 3). Accordingly, the nest
hydroxyl groups are diminished, lowering weak/moderate
Brønsted acidity as shown in Figure 4. The Na-exchanged
Sn-zeolite could further diminish the remained Brønsted
acidity. The active sites in the Sn-β catalyst are those
hydrolyzed active Sn framework, where the hydroxyl groups
on or near the active Sn sites could lead to somewhat
Figure 7. Catalytic activity with Sn-β-Ar-Na (a) and comparison of best
catalytic results with three Sn-β catalysts (b) air: Sn-β, Ar: Sn-β-Ar, Ar-
Na: Sn-β-Ar-Na. reaction conditions: reflux, 350 K, 0.9 mmol Mal, 80
mmol ethanol and 0.5 g Sn-β-Ar-Na.
The stability of Sn-β-Ar-Na zeolite was studied. There is a
gradual deactivation during the four consecutive recycle
runs (Figure S5). However, catalysts can be readily
regenerated by calcination in air for 5 hours at 773 K
(Figure S5). The encouraging results suggest a great
potential for this catalyst in the practical application toward
the simultaneous production of Mol and Dal.
[
22]
Brønsted acidity.
With the sodium ion-exchange step,
those protons near the Sn sites could be readily
[
38]
replaced. Besides, the Na-exchanged deAl-β also shows
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ChemSusChem
10.1002/cssc.201701435
FULL PAPER
a reduced activity as illustrated in Entry 4 of Table 3, which
is due to the fact that the unoccupied nest or surface
hydroxyl groups could also be exchanged, resulting in
weakened Brønsted acidity. Overall, the high conversion
and selectivity over MPV through Lewis acid sites is favored
over the acetalization and addition reactions on Brønsted
acid sites, as referred in Entry 9 and Figure 7b. It should be
noted that the calculated TON numbers referring to the
MPV products (i.e. Mol) produced on each Lewis acid site
are comparable over the 3 Sn-β catalysts as shown in
Table S4, where the numbers of Lewis and Brønsted acid
sites are estimated using the results from ammonia TPD
and pyridine-IR. These results suggest that the superior
performance from Sn-β-Ar-Na compared to that of Sn-β-Ar
and Sn-β is due to the increased number of Lewis acid
sites, which enhances MPV products, and the diminished
Brønsted acid sites, which limits the side reactions. The
mechanism over the complex reaction network will be next
discussed in detail.
the C
6
ether is quite straightforward, as it can be derived
from Mol and ethanol. Ibol generation is more complex; it
can be acquired either directly through reducing C=C bond
of Mol with ethanol hydrogen fragments,
step route, i.e. the first isomerization of Mol to
isobutyraldehyde and subsequent MPV reaction with
ethanol.
[
40]
or via the two-
[
41a, 41b]
6
It should be noted that the yield of C addition product
decreased from 20 to 15% after the replacement of Sn-β
with Sn-β-Ar, and further declined to 10% with Sn-β-Ar-Na.
Dusselier et al. reported that a vinyl group in conjugation
with a carbonyl could easily undergo a 1, 4-nucleophilic
addition with alcohol under homogeneous metal catalysts
like Sn chloride salts, resulting in the apparent anti-
Markovnikov addition to the olefin. Their further
experiments also show that the reaction could be assisted
by Brønsted acidity, as evidenced by the sole use of
[
39]
H
2
SO
4
.
Our results here appear to suggest that the
reaction is catalyzed mainly by Lewis acid sites, but
possibly enhanced somewhat by the coexistence of weak
or moderate Brønsted acid site. As illustrated in Scheme 2,
Table 3. Catalytic activity of Sn-β and other catalysts.[a]
Sele
c.
Yield
[%]
the production of C
sequential steps such as the 1,4-nucleophilic addition,
isomerization and MPV reaction. No such C product occurs
under the case of H-β or deAl-β in entry 2 and 3 of Table 3,
since the last MPV step can’t proceed due to the lack of
strong Lewis acidity derived from framework Sn. However,
the former two steps could be facilitated by moderate or
weak Brønsted acid sites. This is consistent with the overall
yield following the order of Sn-β > Sn-β-Ar > Sn-β-Ar-Na, as
consistent with the diminished Brønsted acidity.
6
addition alcohol involves several
Con
v.
6
Entr
y
Catalyst
[%]
[
%]
C8+acetal
ization
C ad
dition
6
Mol
Dal
Mol
1
2
3
Blank
H-β
-
-
-
-
-
-
-
-
-
-
-
-
-
-
29.6
24.0
26.0
21.0
deAl-β
deAl-β-
Na
4
5
8.7
-
-
-
-
-
-
6.2
-
-
SnO
2
/de
22.9
20.5
Al-β
6
7
8
SnO
Sn-βb
Sn-β-Arb
2
-
-
-
-
-
-
97.2
99.5
73.4
85.4
71.3
85.0
94.7
99.1
4.4
0.8
19.6
14.0
Sn-β-Ar-
Na
9
b
98.9
91.2
90.2
96.6
0.1
9.9
[
a] Reaction conditions: reflux, 350 K, 1 h, 1.8 mmol of Mal, 80 mmol of
ethanol and 0.2 g catalyst. [b] At optimal condition.
Insights into the reaction pathway
Based on the extensive experiments and analysis above,
the proposed reaction network is displayed in Scheme 2. It
is clear that isolated Sn Lewis sites determine MPV
productivity and the Brønsted acid sites can effectively
catalyze the acetalization reaction. The intriguing part is the
Scheme 2. Proposed reaction network involved with the reaction of Mal in
ethanol solvent on Sn-β.
6
third primary product of C addition derived from Mal and
ethanol, which took a significant effort to identify. As shown
in the Scheme, the possible pathway is that the C=C double
Another issue unsolved yet is the effects of Brønsted and
Lewis acid sites on the formation of the acetal products. As
discussed before, the C8+ acetalization product of Mal
appears to be suppressed on catalysts with the reduced
Brønsted acid sites such as catalysts by Ar pre-treatment
bond of Mal is first attacked by ethanol to form C
6
intermediate via 1, 4-addition, staying in equilibrium with its
aldehyde isomer, which is common in reactions catalyzed
[
39]
by homogeneous Sn catalysts.
The latter isomer then
and Na-exchange (in Figure 6 and 7 respectively),
conducts a MPV reaction with ethanol to obtain the alcohol
counterpart and acetaldehyde. The formed aldehyde will
subsequently convert to Dal, which may explain its higher
yield than Mol during the whole reaction time course. This is
further supported by the fact that Dal roughly equals to the
compared to that from the Sn-β (in Figure 5) under 1 h
reaction. However, this may be more related with the
equilibrium between Mal and the acetal products, as more
Mal converted to Mol in the former two cases will result in
less C8+ acetalization product under equilibrium. Indeed, a
high yield of Dal (>95%) is achieved in all of those three
catalysts, regardless of their distinctive Brønsted acid
sum of Mol and C
6 6
addition. C ether and Ibol were seen as
the two minor products derived from Mol. The formation of
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ChemSusChem
10.1002/cssc.201701435
FULL PAPER
properties, indicating that other factor like the Lewis acid
sites should also play an important role in the acetalization.
Acetalization by both Lewis and Brønsted acid has been
sodium exchange, the yield of Mol and Dal both referenced
to Mal reactant reached up to 90% and 96% respectively.
Mol derived from the MPV reaction is believed to be
realized by the Sn Lewis acid sites, while Dal from the
acetalization of acetaldehyde could be catalyzed by both
moderate or weak Brønsted and Lewis acid sites. The Sn-
β-Ar was prepared by pre-heating Sn-β in Ar gas flow
before air calcination (Sn-β-Ar), which diminished the
number of extra-framework Sn species and instead enabled
more Sn species to be exchanged into the framework as
isolated tetrahedral Sn (IV). As a result, the selectivity
toward Mol is enhanced, while the side reactions including
acetalization and addition are restrained. The sodium-
exchanged catalyst can further diminish the weak Brønsted
acid, resulting in a higher yield of desired MPV products.
With extended reaction time, Dal gradually converts back to
form acetaldehyde, which could be evaporated out and
collected in an outside condenser. Mol also slowly reacts to
[
34, 42]
previously reported,
but the role of different acid sites
in the complex catalyst like Sn-β hasn’t been fully clarified
yet according to the best of our knowledge. To further
provide insight into the effect of Brønsted/Lewis acidity on
the acetalization, a simple reaction just using acetaldehyde
and ethanol as the substrates was performed under various
catalysts. Without the complex reactions involved like those
in Scheme 2, the results are quite straightforward and well
distinguished corresponding to the varied acid properties,
as shown in Figure 8. On dealuminated zeolite deAl-β,
which has only weak or medium Brønsted acid sties from its
rich of terminal or defect silanols, 30% yield of Dal was
reached. On Na-exchanged deAl-β-Na (Na exchange once)
and deAl-β-Na3 catalysts (Na exchange 3 times), Dal yields
are significantly reduced to 1.5% and 0.8%, respectively,
due to the nearly complete removal of those weak Brønsted
acid sites by Na-exchange process. In addition, it was also
found that Dal yield reduced from 33% to 23%, when the
working catalyst was switched from Sn-β-Ar to Sn-β-Ar-Na3
catalysts. These results clearly confirm the catalytic role of
Brønsted acidity on Dal formation. On the other hand, Sn-β-
Ar-Na3 catalysts exhibit a high yield of Dal up to 23%,
compared to that of 0.8% from deAl-β-Na3. There will
barely exist any weak Brønsted acid sites in Sn-β-Ar-Na3,
as that in deAl-β-Na3 after three times Na ion exchange.
The strong Lewis acidity due to Sn incorporation in the
former catalyst is thus the only reason responsible for the
consequent higher activity toward the acetalization. Based
on these results, it clearly demonstrates that the
acetalization reaction is not solely catalyzed by Brønsted
acid sites, but also contributed from the Lewis acid sites,
which actually play a dominant role in Sn-β-Ar and its ion
exchanged counterpart. Along with this line, similar
experiments have been conducted to evaluate the
6
form Ibol and C ether. The reaction network of Mal and
ethanol is described over the Sn-β catalysts, and the
mechanistic insight can be of great importance to
understand and manipulate the complex reactions between
ɑ, β-unsaturated aldehydes and primary alcohols.
Moreover, we clearly demonstrate through direct
experimental results that the acid properties of post-
synthetic Sn-beta zeolite can be fine-tuned via simple
pretreatment like Ar-preheating and alkali ion-exchange
process, thus precisely controlling the reaction selectivity
toward the desired products.
Experimental Section
6
mechanism over other minor products including C ether
and isobutanol. As shown in the Figure S6, it appears that
the dominant factor toward the etherification is the
weak/medium Brønsted acid sites remained on the Sn-β or
Sn-β-Ar.
Chemicals and materials
Methacrolein (95%), methallyl alcohol (98%), diethyl acetal
(95%), acetaldehyde (99.5%) were obtained from Aladdin
Reagent Co. Ltd. (Shanghai, China). Tin (II) acetate was
purchased from J&K Chemical Technology. Ethanol,
isopropanol, isobutanol, sodium nitrate, commercial H-β
zeolite (Si/Al=12.5), HNO (65%-68%) were supplied by
3
Sinopharm Chemical Reagent Co. Ltd. (Shanghai, China)
and used without further purification.
Catalyst synthesis
The zeolites Sn-β and Sn-β-Ar were prepared following the
similar methods reported by Hermans and Hammond et
[
20a, 21b]
al.
Specifically, H-β (Si/Al=12.5) was dealuminated
solution (65%-68% HNO , 373 K, 20
by treatment in HNO
h, 20 mL g zeolite). The acid-treated powder was then
filtered, washed thoroughly with deionized water, and dried
3
3
-
1
Figure 8. Acetalization of acetaldehyde with ethanol using different
catalysts. Reaction conditions: 0.8 mmol acetaldehyde, 80 mmol ethanol, at 383 K overnight. The dealuminated zeolite (denoted as
3
50 K, 10 min, 0.1 g catalysts.
deAl-β) was then grafted with tin through the solid-state ion-
exchange (SSIE) method, by grinding with the appropriate
amount of tin (II) acetate in a pestle and mortar. The
obtained mixing powder was finally calcined in tubular
reactor to obtain the working catalysts, namely Sn-β and
Conclusions
Sn-β-Ar. The former one was calcined under air flow at 823
K for 3 h, as described in Hermans’ initial research.[
20a]
The
We have developed an approach to simultaneously
synthesize chemical intermediates Mol and Dal at low
temperatures, employing a SSIE post-synthetic Sn-β. Upon
pre-treating the catalyst with Ar prior to calcination and
latter, labeled as Sn-β-Ar, was heated up to 823 K (10 K
min ramp rate) first in a flow of Ar (3 h) and subsequently
in air (3 h) for a total of 6 h, referenced by their latest
-
1
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ChemSusChem
10.1002/cssc.201701435
FULL PAPER
modified method.[21a, 21b] Sodium exchanged Sn-β-Ar (Sn-β-
acidity via NH
-TPD and the ratio of Lewis to Brønsted acid
3
Ar-Na) was carried out post-synthetically. The calcined Sn-
sites via FTIR of pyridine adsorption, acid concentrations
are calculated and summarized in Table S4.
β-Ar was soaked into a 1.0 M NaNO
3
solution (50 mL g−1
zeolite) and the mixture was stirred at 353 K for 12 h. The
solid sample was recovered by filtration and washed with
distilled water. After being dried at 383 K overnight, the
sample was calcined at 773 K for 5 h. For comparison, the
Diffuse reflectance ultraviolet−visible (UV−vis) spectra of
samples were recorded in the region of 200−400 nm on a
Varian Cary 5000 UV−vis spectrophotometer in Kubelka-
deAl-β supported tin oxides (denoted as SnO
2
/deAl-β) were
also prepared via mechanical mixing of deAl-β with SnO
followed by calcination at 823 K for 12 h.
2
,
Munk units using BaSO
measurements were carried out on Xplora Raman
spectrometer with the 638 nm source.
4
as reference.
Raman
[
28c]
Catalyst characterization
Catalytic Evaluation
The surface areas of the samples were measured by
nitrogen physisorption on a Micromeritics ASAP 2020 M
instrument. Before the adsorption, samples were degassed
at 573 K for 3 h. The total surface area was calculated via
the Brunauer−Emmett−Teller (BET) equation and the
microporous pore volume was determined using the t-plot
method.
The simultaneous synthesis of Mol and Dal was performed
in a 10 ml round-bottom flask immersed in an oil bath,
equipped with a condenser, a thermometer, and a magnetic
stirrer. Typically, 1.8 mmol of methacrolein and 80 mmol of
the ethanol were introduced in the flask with 0.2-0.5 g
catalysts. The mixture was subsequently heated to 350 K
and allowed to react for a defined time under vigorous
stirring. Small aliquots were withdrawn at different time
intervals to investigate the catalytic activity of time-on-
stream. A variety of reaction conditions such as different
alcohols, temperature, catalyst amount, and substrate ratio
were investigated to achieve an optimized yield and
selectivity. The withdrawn samples after filtration were
analyzed by GC-MS with a HP-5 capillary column (30
m×0.25 mm×0.25 μm), and gas chromatography (Thermo
Trace 1310) with a HP-5 capillary column (60 m×0.32
mm×0.25 μm), where 1,4-dioxane served as internal
standard. Note that the yields of Mol and Dal are both
referenced to Mal.
Scanning electron microscope (SEM) was obtained by
Zeiss sigma microscope, with energy dispersive X-ray
spectroscopy (EDS) measurements analyzing the chemical
compositions. X-ray diffraction (XRD) patterns of samples
were recorded on Rigaku UItima IV X-ray diffractometer
o
with CuKα radiation source (40 kV and 30 mA) from 5 to
o
o
6
0 and a scan speed of 2θ=10.0 /min.
Fourier transform infrared (FT-IR) spectra were collected in
transmission mode as KBr pellets using a Nicolet 6700
spectrometer equipped with a DTGS detector. The FT-IR
instrument was also used to collect information for pyridine
adsorption. Briefly, a self-supporting pellet of the sample
was placed in the flow cell and evacuated under reduced
pressure at 673 K for 1 h. After cooling to 373 K, the
samples were saturated with pyridine vapor and then
evacuated at 373 k and 423 K respectively. Spectra were
recorded at the same temperature in the 4000−650 cm−1
range by using co-addition of 32 scans at a resolution of 4
The spent catalysts were recovered for subsequent stability
tests, being first filtered and dried in an oven at 383 K
overnight, followed by calcination in a muffle furnace for 5
-
1
hours at 773 K (5 K min ramp rate).
-
1
Acknowledgements
cm .
This work was supported by the Major Research Plan of
National Natural Science Foundation of China (No. 91545114,
and No. 91545203), the National Natural Science Foundations
of China (No.21576227) the National Thousand Talents
Program of P.R. China, and the 985 Program of the Chemistry
and Chemical Engineering disciplines of Xiamen University.
3 3
NH -temperature-programmed desorption (NH -TPD) was
carried out. Typically, 0.2 g sample was loaded and
pretreated in a quartz reactor with high-purity He (99.999%)
flow at 573 K for 1 h, followed by cooling down to 373 K.
The adsorption of NH
He mixture (5 vol % NH
saturation of the acid sites. Then, the temperature was
3
was performed at 373 K in an NH
3
-
3
) for 2 hours to ensure the
−
1
raised to 1173 K at a rate of 10 K min . During the
desorption process, the desorbed NH was absorbed by
.01 mol L HCl solution and quantified via a counter
3
−
1
0
−
1
titration with 0.01 mol L NaOH solution in the presence of
mixed indicator (0.1% bromocresol green and 0.2% methyl
red). The number of total acid sites titrated by molecular
ammonia was estimated from values using the following
Keywords: Sn-β • Lewis acid • weak Brønsted acid• MPV •
acetalization
-
1
equation: Total acid density (μmol g )= n(NH
)/m, where c is the concentration of HCl solution, V
the volume of HCl solution; c is the concentration of NaOH
solution, V is the volume of NaOH solution and m is the
3
)/m= (c
1
V
1
is
1
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ChemSusChem
10.1002/cssc.201701435
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The Sn-β, pre-calcined in Ar and
treated with sodium-exchange exhibits
the highest selectivity toward the
desired MPV products.
Wenda Hu, Yan Wan, Lili Zhu, Xiaojie
Cheng , Shaolong Wan*, Jingdong Lin
and Yong Wang
Page No. – Page No.
A Strategy for Simultaneous
Synthesis of Methally Alcohol and
Diethyl Acetal with Sn-β
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