Dicyclopentadiene hydroformylation in an aqueous/organic two phase system in the presence of a cationic surfactant

Article abstract of DOI:10.1016/S1872-2067(10)60182-9

Dicyclopentadiene (DCPD) hydroformylation catalyzed by the water soluble rhodium complex RhCl(CO)(TPPTS)₂ (TPPTS: P(m-C₆H ₄SO₃Na)₃) was studied in an aqueous/organic two phase system containing a cationic surfactant. The effects of various reaction parameters such as reaction temperature, catalyst concentration, water soluble phosphine TPPTS or TPPDS (C₆H₅P(m-C₆H ₄SO₃Na)₂), and surfactant structure were examined. The catalytic activity was better with the ligand TPPTS than with TPPDS. The reaction was accelerated by the addition of the cationic surfactant C₁₆H₃₃N(CH₃)₂C_nH _2n+1 Br(n = 1, 8, 12, 16) but the accelerating effect was attenuated with an increase of the n value. In the presence of the surfactant, the DCPD conversion increased initially and then decreased as the rhodium concentration increased in the range of 0.05-5.00 mmol/L. The catalyst containing aqueous phase was reused four times without significant decrease in activity and regioselectivity.

Full text of DOI:10.1016/S1872-2067(10)60182-9

CHINESE JOURNAL OF CATALYSIS
Volume 32, Issue 4, 2011
Online English edition of the Chinese language journal
Cite this article as: Chin J Catal, 2011, 32: 566–571.
RESEARCH PAPER
Dicyclopentadiene Hydroformylation in an Aqueous/Organic
Two Phase System in the Presence of a Cationic Surfactant
PI Xiaodong1, ZHOU Yafen1,2, ZHOU Limei1,2, YUAN Maolin1, LI Ruixiang1, FU Haiyan1,b,CHEN Hua1,a
1Key Laboratory of Green Chemistry and Technology of Ministry of Education, Department of Chemistry, Sichuan University, Chengdu 610064,
Sichuan, China
2College of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, Sichuan, China
Abstract: Dicyclopentadiene (DCPD) hydroformylation catalyzed by the water soluble rhodium complex RhCl(CO)(TPPTS)2 (TPPTS:
P(m-C6H4SO3Na)3) was studied in an aqueous/organic two phase system containing a cationic surfactant. The effects of various reaction
parameters such as reaction temperature, catalyst concentration, water soluble phosphine TPPTS or TPPDS (C6H5P(m-C6H4SO3Na)2), and
surfactant structure were examined. The catalytic activity was better with the ligand TPPTS than with TPPDS. The reaction was accelerated
by the addition of the cationic surfactant C16H33N(CH3)2CnH2n+1Br (n = 1, 8, 12, 16) but the accelerating effect was attenuated with an in-
crease of the n value. In the presence of the surfactant, the DCPD conversion increased initially and then decreased as the rhodium con-
centration increased in the range of 0.05–5.00 mmol/L. The catalyst containing aqueous phase was reused four times without significant
decrease in activity and regioselectivity.
Key words: aqueous/organic two phase system; dicyclopentadiene; hydroformylation; rhodium; surfactant
Dicyclopentadiene (DCPD) hydroformylation produces
mono- and diformyl derivatives, which are hydrogenated to
produce the corresponding carbinols. The carbinols are used as
raw materials for agricultural chemicals, lubricating oil, plas-
ticizer, and also as intermediate materials for pharmaceuticals
and perfumes. For instance, the monocarbinols are valuable
precursors for the synthesis of 4-homoisoteistane derivatives,
which have powerful antiviral activity [1,2]. Since there are
two unsaturated double bonds in its molecular structure, the
products of DCPD hydroformylation are generally very com-
plicated. Nevertheless, the greater reactivity of the more
strained norbornenyl moiety probably directs the reaction
mainly to the 8, 9 double bond [3]. Inamoto and coworkers [3]
found that a rhodium triphenylphosphine complex can catalyze
regioselective hydroformylation under relatively mild condi-
tions, and obtained a mixture of 8- and 9-formyltricyclo
[5,2,1,02,6]dec-3-ene (referred to as MFTD, Scheme 1) with
over 80% yield.
Aqueous/organic two phase hydroformylation can facilitate
the separation of the catalyst from the product. More impor-
tantly, the water solvent is environmentally friendly and meets
the demand for green chemistry. Hydroformylation in the
aqueous/organic two phase system has been extensively stud-
ied. The most successful industrial application is Rh-TPPTS
(TPPTS: P(m-C6H4SO3Na)3) catalyzed propene hydroformy-
lation, namely, the Ruhrchemie Rhône-Poulec (RCH/RP)
process [4,5]. However, a relatively low activity was obtained
with olefins with poor water solubility. There are several ways
1
3
O
2
6
9
8
Rhodium complex
4
H
+ CO + H2
+
5
7
O
MFTD
DCPD
Scheme 1. DCPD hydroformylation catalyzed by a rhodium phosphine complex.
Received 8 October 2010. Accepted 5 January 2011.
aCorresponding author. Tel: +86-28-85412904; Fax: +86-28-85412904; E-mail: scuhchen@163.com
bCorresponding author. Tel: +86-28-85412904; Fax: +86-28-85412904; E-mail: haijianfu@163.com
This work was supported by the National Natural Science Foundation of China (29792074) and the National Basic Research Program of China (973 Program,
G2000048008).
Copyright © 2011, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier BV. All rights reserved.
DOI: 10.1016/S1872-2067(10)60182-9

PI Xiaodong et al. / Chinese Journal of Catalysis, 2011, 32: 566–571
to improve the water solubility of these olefins, such as adding
with a precision digital pressure gauge (Sang Li Electronic
Equipment Factory, Nanjing, China.)
co-solvent [6], co-ligand [7], amphiphilic phosphines [8–11],
modified cyclodextrin [12–14], thermo-regulated phase trans-
fer catalyst [15,16], and surfactants [17–25], to accelerate the
aqueous/organic two phase hydroformylation. However, both
the co-solvent and co-ligand inevitably lead to the loss of the
catalyst. The synthesis of amphiphilic phosphine is usually
tedious. The usage of modified cyclodextrin often provides
poor regioselectivity. Therefore, the addition of a surfactant is
more promising because this is usually commercially available
and the synthesis method is relatively easy. Previously, we
reported [21] that a cationic surfactant can effectively acceler-
ate Rh-TPPTS catalyzed high olefin hydroformylation, espe-
cially when the surfactant concentration is higher than its
critical micelle concentration (CMC). The reason was attrib-
uted to two factors: (1) the formation of the micelle increased
the interfacial area of two phases and solubility of high olefins
in the aqueous phase containing the rhodium complex; (2) the
micelle cationic head groups were oriented towards the aque-
ous phase and formed a positively charged ion layer, which
attracted active rhodium complex anion species to the interfa-
cial layer from the aqueous solution. Thus, the catalyst was
highly concentrated in the interfacial layer and could easily
interact with olefin solubilized in the micelles. DCPD hydro-
formylation usually shows relatively low activity in an aque-
ous/organic two-phase system due to the poor solubility of
DCPD in the water phase. The addition of a cationic surfactant
is a feasible way to accelerate the reaction. However, only few
research works in this area have been reported [26]. There is no
report about the effect of the surfactant structure on DCPD
hydroformylation. In this paper, we carried out DCPD hydro-
1.3 Hydroformylation test
The hydroformylation reactions were performed in a 60 ml
stainless steel autoclave with a magnetic stirrer. Known
amounts of RhCl(CO)(TPPTS)2, TPPTS, DCPD, surfactants,
and water were added into the autoclave. After the autoclave
was evacuated and purged with syngas three times, it was
pressurized with the required volume of syngas (CO/H2 = 1:1)
and held at the desired temperature. After a given reaction time,
the stirring was stopped and the autoclave was cooled quickly
with cold water to ambient temperature.
A HP 1890 series II gas chromatograph (Hewlett Packard,
Palo Alto, CA) equipped with a flame ionization detector was
used for product analysis. The separation was done on a SE-30
(30 m × 0.32 mm) fused silica capillary column.
2 Results and discussion
The product characterization was performed by the GC-MS
instrument. Similarly to the results reported by Inamoto and
coworkers, DCPD hydroformylation produced two major
products, 8- and 9-formyltricyclo [5,2,1,02,6] dec-3-ene. Al-
though the isomers of MFTD were separated on the gas
chromatographic column, their individual identities could not
be determined. We used the letter ‘E’ to denote the earlier
isomer and ‘L’ to denote the later isomer according to the re-
tention time of the isomers.
formylation
catalyzed
by
the
rhodium
complex
2.1 Effect of temperature
RhCl(CO)(TPPTS)2 in an aqueous/organic two phase system.
A strategy for accelerating the reaction by adding the cationic
surfactants C16H33N(CH3)2CnH2n+1Br (n = 1, 8, 12, 16) is pre-
sented. Various reaction factors, such as reaction temperature,
catalyst concentration, type of ligand, and the surfactant
structure were investigated.
The preliminary experiment was carried out at 1.5 MPa ini-
tial syngas in the presence of 1.0 mmol/L cetyltrimethylam-
monium bromide (CTAB). The temperature range from 60 to
140 °C was investigated in order to test the effect of the tem-
perature on DCPD hydroformylation. At temperatures lower
than 80 °C, the DCPD conversion was very low after 1 h reac-
tion time (Table 1, Entries 1 and 2). This increased with tem-
perature increasing. The DCPD was almost completely con-
verted at 120 °C. However, at this temperature the organic
phase exhibited a light yellow color (Table 1, Entry 4), which
indicated a loss of the rhodium complex into the organic phase.
Therefore, the reaction temperature was set at 100 °C in the
following experiments.
1 Experimental
1.1 Materials
The water soluble ligands TPPTS and TPPDS (C6H5P(m-
C6H4SO3Na)2), and the complex RhCl(CO)(TPPTS)2 were
prepared by following published methods [28]. Other reagents
were purchased from commercial sources and used as received.
2.2 Effect of the rhodium complex concentration
1.2 Surface tension experiment
The effect of rhodium complex concentration on DCPD
hydroformylation was tested in the range of 0.05–5.00 mmol/L.
The results are shown in Table 2. With the rhodium complex
The surface tension Ȗ was determined by the maximum
bubble pressure method at 28 °C. The pressure was measured

PI Xiaodong et al. / Chinese Journal of Catalysis, 2011, 32: 566–571
Table 1 Effect of temperature on DCPD hydroformylation
Entry
Temperature (oC)
Conversion of DCPD (%)
Selectivitya (%)
E/Lb
1.2
1.2
1.1
1.2
1.2
Color of the organic phase
colorless
1
2
3
4
5
60
80
17.7
51.1
89.2
99.1
99.3
93.0
93.2
94.6
95.2
95.2
colorless
100
120
140
colorless
light yellow
tea color
Reaction conditions: n(Rh) = 1.0 mmol/L, n(TPPTS)/n(Rh) = 35, n(CTAB) = 1.0 mmol/L, V(H2O) = 3.0 ml, V(DCPD) = 1.0 ml, p(CO+H2) = 1.5 MPa, 1 h.
aSelectivity to 8- and 9-formyltricyclo [5,2,1,02,6] dec-3-ene. bMolar ratio of earlier isomer of MFTD to the latter isomer.
CTAB can effectively increase the linear to branched molar
ratio of the product aldehyde. To investigate the effect of
TPPDS on DCPD hydroformylation, the molar ratio of
TPPDS/TPPTS was varied with the total phosphine to rhodium
ratio at a constant value (35:1). The data is collected in Table 3.
In the case of the phosphine TPPTS or TPPDS used alone, the
ratio of E/L aldehyde was as low as 1.1. When TPPTS and
TPPDS were simultaneously used, a promoting effect on the
E/L aldehyde was observed, although it only increased slightly
(Table 3, Entries 2–8). However, it is worth noting that the
DCPD conversion changed remarkably, as shown in Table 3.
The conversion of DCPD decreased gradually with decreasing
molar ratio of TPPTS/TPPDS. With TPPTS as the ligand,
89.2% of DCPD was hydroformylated in 1 h reaction time. In
contrast, only 44.5% of DCPD was converted into the corre-
sponding aldehyde when TPPDS was used instead. There are
fewer electronic withdrawing groups (–SO3Na) in the TPPDS
ligand than in the TPPTS ligand, and TPPDS is more basic.
The effect of the TPPDS ligand on the DCPD conversion was
in good agreement with the general observation that a more
basic phosphorous ligand resulted in lower activity [29]. The
lower conversion in the case of TPPDS as the ligand perhaps
can also be attributed to the hydrophobic phenyl group in
TPPDS. The phenyl group can penetrate into the posterior layer
of the micelle, and the DCPD solubilized in the micelle need to
Table 2 Effect of the rhodium concentration on DCPD hydroformyla-
tion
Concentration of
Conversion
of DCPD (%)
6.4
Selectivity
(%)
Entry
E/L
Rh (mmol/L)
0.05
1
2
3
4
5
95.2
1.1
1.2
1.2
1.1
1.1
0.10
20.5
92.6
0.50
97.5
95.3
1.00
89.2
94.6
5.00
73.3
94.2
Reaction conditions are the same as in Table 1.
concentration at 0.05 mmol/L, only 6.4% of DCPD was con-
verted in 1 h (Table 2, Entry 1). This suggested that a sufficient
rhodium complex concentration was required to ensure an
acceptable activity. The conversion was increased significantly
to 97.5% when the concentration of the rhodium complex was
increased to 0.5 mmol/L. This can be attributed to more reac-
tion active sites available with increased rhodium complex
concentration. However, the further increase of the concentra-
tion led to a decrease in the activity. The reason was probably
due to the large amount of TPPTS added to the system to
maintain the molar ratio of TPPTS/Rh at a fixed value (in this
case, TPPTS/Rh = 35). The TPPTS concentration was as high
as 175 mmol/L when the rhodium complex concentration was
increased to 5 mmol/L. Due to its high ionic charge, TPPTS
dissolved in the aqueous phase was detrimental to the stability
of the CTAB micelle. CMCs of CTAB in the different systems
were evaluated by a surface tension technique. The experi-
ments were carried out at 28 °C, and the CMCs of CTAB were
1.1, 0.9, and 2.7 mmol/L, respectively, in the three different
systems (Fig. 1). For the system with the RhCl(CO)(TPPTS)2
concentration of 5.0 mmol/L and TPPTS/Rh molar ratio at 35,
the increased CMC may be responsible for the lower reaction
rate. The CTAB concentration in this catalysis system was only
1.0 mmol/L, which was far lower than the CMC (2.7 mmol/L)
and therefore it could not accelerate the reaction effectively.
43
41
39
37
(1)
35
(3)
(2)
33
0
1
2
3
4
2.3 Effect of the phosphine ligand
CTAB concentration (mmol/L)
Fig. 1. Surface tension profiles of aqueous solutions of CTAB contain-
ing different amounts of RhCl(CO)(TPPTS)2 and TPPTS. (1) CTAB
aqueous solution; (2) CTAB aqueous solution containing 0.5 mmol/L of
RhCl(CO)(TPPTS)2 and 17.5 mmol/L of TPPTS; (3) CTAB aqueous
solution containing 5.0 mmol/L of RhCl(CO)(TPPTS)2 and 175.0 mmol/L
of TPPTS.
Apart from reaction parameters such as temperature and
catalyst concentration, the ligand present can also influence the
reaction. We previously reported [20] that the addition of
TPPDS into the RhCl(CO)(TPPTS)2-TPPTS catalyzed
1-dodecene hydroformylation system containing the surfactant

PI Xiaodong et al. / Chinese Journal of Catalysis, 2011, 32: 566–571
Table 3 Effect of molar ratio of TPPTS to TPPDS on DCPD hydrofor-
mylation
P
n(TPPTS)/
n(TPPDS)
TPPTS
10:1
Conversion
(%)
Selectivity
(%)
Entry
E/L
P
1
2
3
4
5
6
7
8
9
89.2
94.6
1.1
1.4
1.4
1.3
1.2
1.3
1.3
1.3
1.1
More crowded
environment
88.0
95.0
7.5:1
86.1
93.7
5:1
85.8
94.5
1:1
86.7
94.6
1:5
75.7
94.2
1:7.5
70.7
94.1
1:10
63.8
94.0
TPPDS
44.5
93.1
Reaction conditions are the same as in Table 1 except n(TPPTS+TPPDS)/
n(Rh) = 35.
SO3
overcome the steric hindrance resulting from the phenyl group
of TPPDS before it can reach the interface to coordinate with
the rhodium active center (Fig. 2). Therefore, the reaction was
slowed down.
:
CTAB
:
Fig. 2. Sketch of the possible position of TPPDS and TPPTS in CTAB
micelles and the effect on DCPD hydroformylation.
2.4 Effect of the surfactant structure
were tested. The results are shown in Table 4. The DCPD
conversion decreased as the n value in –CnH2n+1 increased from
1 to 16. This was completely different from the observation in
the long chain olefin hydroformylation system. In the latter
case, the long chain olefin conversion increased with the
lengthening of the alkyl chain –CnH2n+1 [16]. This was ex-
plained by that the double long chained surfactant
C16H33N(CH3)2CnH2n+1Br (n = 12, 16) can form a vesicle,
which not only can dissolve more olefin, but also can enlarge
the interface to a larger extent than the micelle formed by
CTAB. Consequently, the double long chained surfactant can
accelerate the reaction much significantly. As compared with a
flexible long chain olefin, it is more difficult for the more
sterically demanding DCPD to move to the interface from the
hydrophobic region. Furthermore, the alkyl group –CnH2n+1
may block the contact of the catalyst with DCPD more with the
lengthening of the alkyl chain (Fig. 3).
The effect of the surfactant on the reaction was also exam-
ined. Without CTAB, only 41.0% of DCPD was converted after
reaction for 1 h under 2.0 MPa syngas pressure, which was
much lower than the conversion in the presence of CTAB
(98.2%) (Table 4, Entry 2). For comparing with CTAB, a series
of cationic surfactant C16H33N(CH3)2CnH2n+1Br (n = 8, 12, 16)
Table 4 Effect of surfactant on DCPD hydroformylation
Conversion Selectivity
Entry
Surfactant
E/L
(%)
41.0
98.2
89.4
81.9
74.1
(%)
94.6
93.0
94.3
94.6
93.9
1
2
3
4
5
—
1.2
1.1
1.1
1.0
1.1
C16H33N(CH3)2CH3Br
C16H33N(CH3)2C8H17Br
C16H33N(CH3)2C12H25Br
C16H33N(CH3)2C16H33Br
Reaction conditions are the same as in Table 1 except p(CO+H2) = 2.0
MPa.
CTAB
organic phase
C16H33NCnH2n+1Br
n = 2, 8, 12, 16
anionic rhodium catalytic species
Rh
Rh
B
Rh
A
more crowded environment
aqueous phase
Fig. 3. Illustration of the effect of surfactant structure on DCPD hydroformylation.

PI Xiaodong et al. / Chinese Journal of Catalysis, 2011, 32: 566–571
and ligand.
Table 5 Catalyst recycle tests
Recycling
CTAB/TPPTS
(mg/mg)
—
Conversion
(%)
Selectivity
(%)
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95.2
93.9
1.2
1.2
1.2
1.2
1.2
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2
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