Zeolites as Shape-Selective Catalysts: Highly Selective Synthesis of Vanillin from Reimer-Tiemann Reaction of Guaiacol and Chloroform

Article abstract of DOI:10.1007/s10562-014-1456-5

Reimer-Tiemann reaction of guaiacol and chloroform was carried out in the presence of various zeolites. Vanillin was afforded as major product in a high selectivity. Zeolites played an important role of shape-selective catalysts in the reactions. Among the examined zeolites, ZSM-5 showed the best result to give the desired product vanillin in 85 % selectivity and 58 % yield. Graphical Abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s10562-014-1456-5

Catal Lett
DOI 10.1007/s10562-014-1456-5
Zeolites as Shape-Selective Catalysts: Highly Selective Synthesis
of Vanillin from Reimer–Tiemann Reaction of Guaiacol
and Chloroform
Shenyong Ren
Baojian Shen
•
Zhenhua Wu
•
Qiaoxia Guo
•
Received: 13 October 2014 / Accepted: 25 November 2014
Ó Springer Science+Business Media New York 2014
Abstract Reimer–Tiemann reaction of guaiacol and
chloroform was carried out in the presence of various
zeolites. Vanillin was afforded as major product in a high
selectivity. Zeolites played an important role of shape-
selective catalysts in the reactions. Among the examined
zeolites, ZSM-5 showed the best result to give the desired
product vanillin in 85 % selectivity and 58 % yield.
Europe and US legislation, however the high costs and
complicated process limit its industrial manufacture and
only one commercial biotech product is present in the
market till now [9–13]. Hence people’s requirement for
vanillin still mainly relies on chemical methods [14–20].
Among the chemical processes, Reimer–Tiemann reaction
of guaiacol and chloroform is the simplest route which
involves only one step to synthesize vanillin. The main
drawback of Reimer–Tiemann reaction is the selectivity of
products where a mixture of major o-vanillin and minor
vanillin is usually afforded as shown in Scheme 1 [21, 22].
Porous zeolites have been utilized as shape-selective
catalysts in many synthetic reactions and industrial pro-
duction because only the compounds with proper dimen-
sions can pass through the catalyst pores [23–26]. Recently
we had reported a benzylation reaction of anisole and
benzyl halide in the presence of zeolites. The para-product
was selectively formed as major product due to the shape-
selective effect of zeolites [27]. The result of benzylation
prompted us to investigate Reimer–Tiemann reaction under
shape-selective catalysis since the porosity of zeolites
could inhibit the formation of ortho-product with bigger
steric hindrance. In this paper we would like to describe
highly selective synthesis of vanillin from Reimer–Tie-
mann reaction of guaiacol and chloroform in the presence
of zeoltites as shown in Scheme 2.
Keywords Reimer–Tiemann reaction Á Guaiacol Á
Vanillin Á Shape-selective catalyst Á Zeolite
1
Introduction
Vanillin is widely used as flavor in the food, cosmetic, and
as intermediate in the pharmaceutical, nutraceutical and
fine chemical synthesis with an annual world production of
about 12,000 t/year [1–6]. Natural vanillin is produced
from the beans of the orchid Vanilla planifolia by a mul-
tistep curing process, but the amount of natural vanillin can
only satisfy less than 1 % of the demand [7, 8]. This has
resulted in the substitution of synthetic vanillin for natural
vanillin in most applications. Biotechnological production
of vanillin can be labeled as a ‘‘natural flavor’’ under
S. Ren (&) Á Z. Wu Á B. Shen (&)
State Key Laboratory of Heavy Oil Processing, College of
Chemical Engineering, China University of Petroleum, No. 18
Fuxue Road, Changping District, Beijing 102249, China
e-mail: shenyong@cup.edu.cn
2 Results and Discussion
B. Shen
e-mail: baojian@cup.edu.cn
We found when the reaction of guaiacol, chloroform and
sodium hydroxide was carried out at room temperature for
2
4 h, a mixture of 33 % o-vanillin and 14 % vanillin was
Q. Guo
College of Science, China University of Petroleum, No. 18
Fuxue Road, Changping District, Beijing 102249, China
formed (Table 1, Entry 1). The by-product o-vanillin was
major. Interestingly addition of microporous zeolite Y to
123

S. Ren et al.
OH
Table 2 Temperature effect in the reaction of guaiacol and chloro-
form with ZSM-5
OH
OH
OMe
OMe
NaOH
OHC
OMe
+
+
CHCl3
Entry Temp (°C) Yield of 2 (%) Yield of 3 (%) Ratio of 2:3
CHO
1
2
3
Rt
4
38
61
28
33
35
1:7.0
1:0.9
1:0.6
1
2 o-vanillin
major)
3 vanillin
(
(minor)
50
Reflux
Scheme 1 Reimer–Tiemann reaction of guaiacol
The reactions were carried out for 6 h and detected by GC
OH
OH
OH
OMe
OMe
NaOH
zeolite
OHC
OMe
+
were analogous to the dynamic diameters of guaiacol and
vanillin.
+
CHCl3
To shorten the reaction time and increase the yield of
product, we tested the temperature effect in the reaction of
guaiacol and chloroform in the presence of zeolite ZSM-5.
The results were showed in Table 2. Unfortunately, with
the increasing of reaction temperature, the selectivity of
products became poorer and poorer. The yield of by-
product o-vanillin was gradually increased to be a major
product, although the conversion of guaiacol was quanti-
tative at high temperature in a short time.
CHO
3 vanillin
(major)
1
2 o-vanillin
minor)
This work
(
Scheme 2 Reimer–Tiemann reaction of guaiacol in the presence of
zeolite
Table 1 Products distribution of Reimer–Tiemann reaction in the
presence of zeolites
Entry Zeolite
Yield of 2 (%) Yield of 3 (%) Ratio of 2:3
Selective Reimer–Tiemann reactions by using cyclo-
dextrin as shape-selective catalyst were reported. The high
selectivity was attributed to the formation of a ternary
molecular complex composed of cyclodextrin, chloroform
and phenol in the reaction mixture. Phenol penetrated the
cavity of cyclodextrin from the side involving the para-
carbon atom which was individually allowed to be attacked
by dichlorocarbene [28–30]. In our reactions, the guaiacol
and chloroform molecules could be also located in the hole
of microporous zeolites by adsorption as shown in
Scheme 3. Dichlorocarbene which was generated by the
reaction of chloroform and NaOH attacked at the para-
position of guaiacol to give the desired product vanillin
after hydrolysis. Probably the shape-selectivity effect was
derived from the pore mouth-limitation since the molecular
size of guaiacol and vanillin were bigger than the pores
diameter of ZSM-5 where guaiacol could not enter inside
of the pores. On the other hand, the effect of the isomeri-
zation reaction from the extra-surface catalysis of zeolite
ZSM-5 could also affect the shape-selectivity. The attacks
at otho- or meta-positions of guaiacol were blocked
intensively by the channel wall of zeolites. The formation
of by-product o-vanillin was attributed to the adsorption of
guaiacol on the external surface of zeolites or free guaiacol
in the solution.
1
2
3
4
5
6
7
8
9
None
Y
33
21
10
14
14
34
58
56
37
41
34
47
26
1:0.4
1:1.6
1:5.8
1:4.0
1:2.1
1:3.1
1:1.5
1:2.9
1:0.7
ZSM-5
ETS-10
SAPO-34 18
Beta 13
Mordenite 22
ITQ-13
16
35
MCM-41
The reactions were carried out at room temperature for 24 h and
detected by GC
the reaction afforded 21 % of o-vanillin and 29 % of
vanillin (Table 1, Entry 2). The ratio of o-vanillin to van-
illin was changed significantly in sharp contrast to the
none-zeolite reaction. Then various zeolites such as
microporous ZSM-5, ETS-10, SAPO-34, Beta, Mordenite,
ITQ-13, and mesoporous MCM-41 were employed to the
reaction respectively to study the selectivity. The results
were showed in Table 1. Among the examined zeolites,
microporous ZSM-5 is the best shape-selective catalyst
which gave a ratio of o-vanillin to vanillin as 1:5.8 and
5
8 % yield of vanillin (Entry 3). Other microporous zeo-
lites also showed good selectivity in the reactions to give
desired vanillin as major product (Entry 4–8). MCM-41
which is mesoporous zeolite with more than 2 nm pore
diameter showed poor selectivity in the reaction (Entry 9).
Probably the pore size of MCM-41 is too big to restrict the
formation of o-vanillin. Nevertheless the microporous
zeolites possessed abundant less than 1 nm pores which
3 Conclusions
In summary, we selectively synthesized vanillin through
the Reimer–Tiemann reaction of guaiacol and chloroform
in the presence of zeolites as shape-selective catalyst. This
1
23

Zeolites as Shape-Selective Catalysts
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