Consecutive addition esterification and hydrolysis of cyclic olefins catalyzed by multi-SO3H functionalized multi heteropolyanion-based ionic hybrids undersolvent-free conditions

Article abstract of DOI:10.1080/00397911.2019.1580743

An efficient protocol for the synthesis of cycloalkyl carboxylates and alcohols from cyclic olefins is described. The cyclic olefins were converted to corresponding target molecules under solvent-free conditions catalyzed by two novel multi-SO₃H functionalized multi heteropolyanion-based ionic hybrids through one-pot consecutive addition esterification and hydrolysis reactions. This approach has several advantages, including high yield, simple workup and simple purification.

Full text of DOI:10.1080/00397911.2019.1580743

Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic
Chemistry
ISSN: 0039-7911 (Print) 1532-2432 (Online) Journal homepage: https://www.tandfonline.com/loi/lsyc20
Consecutive addition esterification and hydrolysis
of cyclic olefins catalyzed by multi-SO3H
functionalized multi heteropolyanion-based ionic
hybrids undersolvent-free conditions
Guocai Zheng & Xinzhong Li
To cite this article: Guocai Zheng & Xinzhong Li (2019): Consecutive addition esterification
and hydrolysis of cyclic olefins catalyzed by multi-SO3H functionalized multi heteropolyanion-
based ionic hybrids undersolvent-free conditions, Synthetic Communications, DOI:
10.1080/00397911.2019.1580743
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SYNTHETIC COMMUNICATIONSV
https://doi.org/10.1080/00397911.2019.1580743
Consecutive addition esterification and hydrolysis of cyclic
olefins catalyzed by multi-SO3H functionalized multi
heteropolyanion-based ionic hybrids under
solvent-free conditions
Guocai Zhenga,b and Xinzhong Lia,b,c,d
aDepartment of Materials Engineering, Ocean College, Minjiang University, Fuzhou, People’s Republic of
b
China; Green Dyeing and Finishing Engineering Research Centre, Fujian University, Fuzhou, People’s
Republic of China;cState Key Laboratory of Structural Chemistry, Fuzhou, People’s Republic of
China;dFujian Engineering Research Center of New Chinese Lacquer Material, Fuzhou, People’s Republic
of China
ABSTRACT
ARTICLE HISTORY
Received 8 March 2018
An efficient protocol for the synthesis of cycloalkyl carboxylates and
alcohols from cyclic olefins is described. The cyclic olefins were con-
verted to corresponding target molecules under solvent-free condi-
tions catalyzed by two novel multi-SO3H functionalized multi
heteropolyanion-based ionic hybrids through one-pot consecutive
addition esterification and hydrolysis reactions. This approach has
several advantages, including high yield, simple workup and simple
purification.
KEYWORDS
Addition esterification;
cyclic olefins;
heteropolyacid;
ionic hybrids
GRAPHICAL ABSTRACT
[8S3SiIH]
Yield: 44-93%
O
O
R
R
O
[6S2PIH]
+
O
+
R
OH
Solvent-free
O
-H
R =
N
N
SO H
3
=
-CH3
SO H
3
[8S3SiIH]
or
[6S2PIH]
H2O
-CH2CH3
SO H
3
N
N
N
=
SO H
3
-CH2CH2CH3
= SO3H
OH
OH
+
Yield: 88%
Yield: 87%
CONTACT Xinzhong Li
lixinzhong@mju.edu.cn;lixinzhong77@126.com
Department of Materials Engineering,
University of Minjiang, No. 200 Xiyuangong Road, Shanjie, Minhou, Fuzhou, 350108, China.
Supplemental data for this article is available online at on the publisher’s website.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lsyc.
ß 2019 Taylor & Francis Group, LLC

2
G. ZHENG AND X. LI
Introduction
Polyoxometalates (POMs) are a large series of discrete and stable nanoscaled anionic
metal oxide clusters with well-defined molecular structures, which have achieved wide
applications in the areas of catalysis, material science, medicine.[1] Since their chemical
and physical properties can be finely tuned by choosing constituent elements and coun-
tercations, hybrid organic–inorganic POMs which are a combination of the inorganic
POMs with specific organic functional groups have been designed. Based on this modi-
fication strategy, a series of new materials based on POMs were developed with interest-
ing properties, such as redox activities, Brꢀnsted acid, optic, and magnetism, etc.[2]
Among the various reported methods, ionic self-assembly strategy provides a promising
route owing to the relative convenience and universality of synthesis.[3] For example,
surfactant-encapsulated polyoxometalate,[4] dendritic polyoxometalate hybrids,[5] func-
tionalized heteropolyanion–based ionic liquids or ionic hybrids[6–8] have been reported,
which acted as green heterogeneous or homogeneous catalysts and have been studied
extensively in epoxidation of alkenes,[9–10] alcohol/ketone selective oxidation,[11–13]
esterification,[14–16] acetylation,[17] nitration,[18] deep desulfurization,[19] Knoevenagel
condensation,[8] and C–C coupling reactions.[20]
Cyclohexyl and cyclopentyl carboxylates are high-value-added fine chemicals widely
used in perfume, pharmaceutical, organic synthesis, and coating industries.[21]
Nowadays, with the increasing environmental concerns and more stringent regulations
in industry, and the availability of cyclohexene on a large scale, direct addition esterifi-
cation of cyclohexene with carboxylic acid have been developed catalyzed by sulfonated
carbon,[22] sulfonic acid modified mesostructured silica,[23] sulfated zirconia, acidic ion
exchange resins,[24] and Brꢀnsted acidic ionic liquids.[25] Compared to the Fischer
esterification, these reports showed attractive advantages, such as atom economy, simple
workup, time-saving, low cost, high conversion, and selectivity, etc.
Herein, we presented a green, efficient, and consecutive approach for direct addition
esterification of cyclohexene with the carboxylic acid, using two novel multi-SO3H func-
tionalized multi-heteropolyanion-based POM ionic hybrids 8S3SiIH and 6S2PIH
(Scheme 1) as heterogeneous catalysts in one-pot under solvent-free conditions. The
corresponding cycloalkyl carboxylates were produced with yields of 44–93%. Upon sub-
sequent addition of water, cyclohexanol and cyclopentanol were obtained with yields of
87% and 88%, respectively. Two ionic hybrids can be reused for up to eight times after
simple filtration and without a noticeable decrease in their activity.
Results and discussion
Initially, the addition esterification of cyclohexene with acetic acid under solvent-free
conditions was examined. Under optimal conditions, the results are listed in Table 1
(Entry 2). Cyclohexyl acetate was obtained with a yield of 82% and 75%, respectively.
Based on this success, the generality of this synthetic strategy was investigated, and the
results are shown in Table 1. Cyclohexenes, cyclopentenes were transformed into the
corresponding esters successfully with moderate to excellent yields, for straight chain
terminated olefin 1-octene, a mixture of three isomers of octyl acetates were obtained.

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3
[8S3SiIH]
[6S2PIH]
Yield: 44-93%
O
O
R
R
O
+
O
+
R
OH
Solvent-free
O
-H
R =
N
N
SO H
3
=
-CH3
SO H
3
[8S3SiIH]
or
[6S2PIH]
H2O
-CH2CH3
SO H
3
N
N
N
=
SO H
3
-CH2CH2CH3
= SO3H
OH
OH
+
Yield: 88%
Yield: 87%
Scheme 1. Consecutive addition esterification and hydrolysis of cyclic olefins with carboxylic acids
catalyzed by two novel multi-SO3H functionalized multi heteropolyanion-based ionic hybrids under
solvent-free conditions.
The esterification of cyclohexane with formic acid with various control catalysts were
also investigated, these results are listed in Table 2. Compared to acidic ionic liquids
[(CH2)3SO3Hmim]HSO4, H4SiW12O40, H3PW12O40 and solid acid Amberlyst-15, two
ionic hybrids gave the highest yield, their high catalytic activities in esterification could
be ascribed to the following facts: (1) The high acidity and acid content. With the
increasing of acidity, the protonation capacity of catalyst improves accordingly. So single
SO3H-functionalized [(CH2)3SO3Hmim]HSO4 showed higher catalytic activity than
[bmim]HSO4, but lower than Amberlyst-15, 8S3SiIH and 6S2PIH. (2) The nanosized
amphiphilic surface of two ionic hybrids, which provided
a
suitable
microenvironment for olefin and carboxylic acids were absorbed and react on the cata-
lytic sites (Figure 1).
Stability and reusability are important for developing catalytic system with industrial
potential, the reusability of 8S3SiIH and 6S2PIH for esterification of acetic acid with
cyclohexane were investigated, the results are summarized in Figure 2, two ionic hybrids
could be quantitatively recovered from the reaction mixture and reused eight times
without significant loss in conversion and selectivity. Moreover, the TG curve, IR spec-
tra, and acidity of recycled ionic liquids were also determined and it was found that
there were no obvious differences between recycled and fresh samples. These results
indicate that 8S3SiIH and 6S2PIH are stable catalysts in the reaction system.

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G. ZHENG AND X. LI
Table 1. Results of esterification of olefin with carboxylic acids catalyzed by 8S3SiIH and 6S2PIHa.
Carboxylic acid
Olefin
Yield b˄%˅
Entry
Temp.ꢀćꢁ
Product
O
H
1
HCOOH
95
90 c/81 d
O
O
CH3
2
3
CH3COOH
110
120
82 c /75d
62c /57 d
O
O
C2H5
CH3CH2COOH
O
O
C3H7
4
5
CH3CH2CH2COOH
HCOOH
130
95
51c /44 d
93c/85 d
O
O
H
O
O
O
O
CH3
C2H5
C3H7
6
7
8
9
CH3COOH
110
120
130
120
84 c /79d
68 c /61d
57c /50d
42c /36d
O
O
CH3CH2COOH
CH3CH2CH2COOH
CH3COOH
O
O
O
O
10
11
CH3COOH
120
87c /79d
O
O
53c /47d
38c /30d
˘5 c, d
H3C
H3C
O
O
CH3COOH
110
O
O
H3C
O
aReaction conditions: catalyst (0.45 mmol), 75 mmol acid, 30 mmol olefine, 4 h.
bIsolated yields.
cResults of 8S3SiIH; dResults of 6S2PIH.

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Table 2. Esterification of with cyclohexene with formic acid catalyzed by different catalystsa,b
.
Catalyst
Product
Conv. (%)
Yield (%)
O
H
—
—
—
O
O
O
H
H
[(CH2)3SO3Hmim]HSO4
52
40
34
82
50
34
31
74
O
O
H4SiW12O40
O
H
H3PW12O40
O
O
H
Amberlystϋ15
O
aReaction conditions: 30 mmol cychexene, 90 mmol formic acid, 120 ꢁC, 4 h.
bfor solid acid catalyst which loading is 0.13 g/mL cychexene; for [(CH2)3SO3Hmim]HSO4 which usage is 10 mmol.
Figure 1. SEM photograph of 8S3SiIH (left) and 6S2PIH (right).
A plausible mechanism for the formation of a carbocation intermediate mechanism
could be proposed. In the initial step, olefins were protonated by sulfonic acid groups
on the ionic hybrids and gave the carbocation, which undergoes a nucleophilic attack of
carboxylic acid to carbocation and generated oxonium ion intermediate. Finally, the
esters were formed by deprotonation of the oxonium ion ions, and the catalyst is then
regenerated. Being electrophilic addition, significantly affected by the steric hindrance,
the straight chain alkene gave a low yield of ester than cycloolefin for its higher steric
hindrance. Moreover, using straight chain alkene acted as a substrate, the intermediates
are stable secondary and tertiary carbonations formed by carbocations rearrangement,
resulting in a mixed product and a remarkable decline in yields. In addition, 8S3SiIH
gave better results than 6S2PIH for its higher acidity and acid content.

6
G. ZHENG AND X. LI
8S3SiIH
6S2PIH
100
80
60
40
20
0
1
2
3
5
6
7
8
4Run
Figure 2. Reusability of 8S3SiIH and 6S2PIH.
Nowadays, the cyclohexanol was usually manufactured by phenol hydrogenation or
cyclohexane oxidation in industry. These methods suffer from high cost of raw materi-
als, high pressure and temperature, poor selectivity and yields and so on. Based on the
success of direct addition esterification of cyclohexane and cyclopentane with a series of
carboxylic acids, the subsequent hydrolysis of the carboxylates was studied. With the
addition of water in the presence of 8S3SiIH and 6S2PIH, hydrolysis of carboxylates
took place smoothly and cyclohexanol with the yield of 87% was obtained (Table 3,
Entry 2).
Experimental
Synthesis of 8S3SiIH and 6S2PIH
The mixture of tetramethylethylenediamine or pentamethyldiethylenetriamine (1 mol)
and 1, 3-propyl sulfone (1.05 mol) in CH3CN(50 mL) were charged into a three-
necked flask in an oil bath at 45 ꢁC with stirring under a nitrogen atmosphere.
After 24 h, the reaction mixture was cooled to room temperature, the ꢁresulting
precipitate was filtered, and washed with diethyl ether. After drying at 65 C under
vacuum for 8–10 h, the corresponding precursor zwitterionic salt L1 and L2 were
obtained with a yield of 95% and 97%, respectively. After the zwitterionic salt (2.0
mmol) was thoroughly dissolved in 35 mL deionized water, H4SiW12O40 (1.5 mmol)
or H3PW12O40 (1.33 mmol) aqueous solution was added dropwise under stirring
conditions, the mixture was stirred at room temperature for 24 h, the resulted ionic
hybrids were collected by filtration and washed repeatedly with water to remove any
unbonded POM, then dried under vacuum at 80 ꢁC for 8 h to afford 8S3SiIH
and 6S2PIH.

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7
Table 3. Results of hydrolysis of cyclic carboxylic esters catalyzed by 8S3SiIH and 6S2PIHa.
Yield b˄%˅
Entry
Ester
Temp.ꢀćꢁ
Product
1
100
87 c/82 d
O
H
OH
O
O
O
CH3
2
3
4
100
100
100
85 c/80d
88c/83 d
OH
O
H
OH
O
O
CH3
OH
85c/80 d
O
aReaction conditions: catalyst (0.5 mmol), 35 mmol cyclic carboxylic ester, 450 mmol H2O, 6 h.
bIsolated yields.
cResults of 8S3SiIH; dResults of 6S2PIH.
Esterification of cyclic olefins with carboxylic acid
8S3SiIH or 6S2PIH (0.5 mmol), cyclic olefin (35 mmol) and carboxylic acid (15 mmol)
were added successively in a 25 mL autoclave equipped with a magnetic stirrer, and
heated to reaction temperature. On completion, the autoclave was cooled to room tem-
perature, after the hybrids were separated by centrifugation, the liquid phase was
extracted with diethyl ether, the combined organic layer was washed successively
with 5% aqueous NaHCO3 solution and deionized water, dried over sodium sulfate, and
concentrated in vacuum to give the corresponding esters. Quantitative analyses were
conducted with a HP1790GC (Agilent Technologies, USA) equipped with a FID
detector and a capillary column HP-5(30 m  0.32 mm  1 lm).
Consecutive direct esterification and hydrolysis of cyclic olefins
8S3SiIH or 6S2PIH (0.5 mmol), cyclic olefin (35 mmol) and carboxylic acid (15 mmol)
were added successively in a 25 mL autoclave equipped with magnetic stirrer, and
heated to reaction temperature for4 h, after the autoclave was cooled to room tempera-
ꢁ
ture, H2O (195 mmol) was added, and the mixture was heated to 100 C for another 6
h. On completion, the hybrids were separated by centrifugation, the liquid phase was
extracted with diethyl ether, the combined organic layer was washed successively with
5% aqueous NaHCO3 solution and deionized, dried over sodium sulfate, and concen-
trated in vacuum to give cyclohexanol and cyclopentanol. Quantitative analyses were
conducted with a HP 1790 GC equipped with a FID detector and a capillary column
HP-5(30 m  0.32 mm  1 lm).
Conclusion
In conclusion, we have developed a green and efficient approach for synthesis of cyclic
carboxylic esters and cyclohexanol and cyclopentanol through consecutive addition

8
G. ZHENG AND X. LI
esterification hydrolysis of cyclic olefins with carboxylic acid under solvent-free condi-
tions using two novel multi-SO3H functionalized multi heteropolyanion-based ionic
hybrids as recyclable heterogeneous catalysts. Several noteworthy features of this
approach including products of ester or alcohol can be selected, two ionic hybrids can
be prepared easily with high purity and low cost, atom economy, high yield, simple
workups and purification procedure, which make it potentially applicable in industry.
Funding
The authors thank the Natural Science Foundation of Fujian Province [No. 2016J01690,
2017J01584], Research Project of Fujian Province Education Department [No.JAT160373, 170453,
and JK2016035], Open Subject of State Key Laboratory of Structural Chemistry [20170030], and
Research Project of Minjiang University [No.MYK18004, 16003, and 16004] for financial support.
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