Nonaqueous Biphasic Hydroformylation of Long Chain Alkenes Catalyzed by Water Soluble Phosphine Rhodium Catalyst with Polyethylene Glycol Instead of Water

Article abstract of DOI:10.1007/s10562-017-2247-6

Abstract: The application of polyethylene glycol (donated as PEG), as an environmentally benign solvent instead of water, in rhodium catalyzed hydroformylation of long chain alkenes by using water soluble phosphine BISBIS or TPPTS (TPPTS: sodium salt of sulfonated triphenylphosphine, BISBIS: sodium salt of sulfonated 2,2′-bis(diphenylphosphinomethyl)-1,1′-biphenyl) is herein reported. The conversion of long chain alkenes in PEG-200 could reach above 95.0% after a short reaction time (15?min). In addition, an efficient phase separation and recycling of PEG-200 and catalyst were achieved. The leaching of rhodium into product phase detected by ICP-AES was less than 0.06?wt% of the initial amount. Graphical Abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s10562-017-2247-6

Catalysis Letters (2018) 148:438–442
https://doi.org/10.1007/s10562-017-2247-6
Nonaqueous Biphasic Hydroformylation of Long Chain Alkenes
Catalyzed by Water Soluble Phosphine Rhodium Catalyst
with Polyethylene Glycol Instead of Water
1
1
1
1
1
1
1
1
Yuanjiang Zhao · Yanli Liu · Jianzhang Wei · Haiyan Fu · Xueli Zheng · Maolin Yuan · Ruixiang Li · Hua Chen
Received: 16 August 2017 / Accepted: 3 November 2017 / Published online: 24 November 2017
©
Springer Science+Business Media, LLC, part of Springer Nature 2017
Abstract
The application of polyethylene glycol (donated as PEG), as an environmentally benign solvent instead of water, in rhodium
catalyzed hydroformylation of long chain alkenes by using water soluble phosphine BISBIS or TPPTS (TPPTS: sodium
salt of sulfonated triphenylphosphine, BISBIS: sodium salt of sulfonated 2,2′-bis(diphenylphosphinomethyl)-1,1′-biphenyl)
is herein reported. The conversion of long chain alkenes in PEG-200 could reach above 95.0% after a short reaction time
(
15 min). In addition, an efficient phase separation and recycling of PEG-200 and catalyst were achieved. The leaching of
rhodium into product phase detected by ICP-AES was less than 0.06 wt% of the initial amount.
Graphical Abstract
Keywords Polyethylene glycol · Hydroformylation · Long chain alkene · Water soluble phosphine · Rhodium
1
Introduction
Hydroformylation is a reaction route for olefins toward alde-
hydes with 100% atom economy and has been developed into
one of the most important homogeneous catalytic processes
*
Maolin Yuan
cdscyml@sina.com
[
1–3]. The global production capacity of aldehydes is beyond
1
Key Lab of Green Chemistry and Technology, Ministry
of Education, College of Chemistry, Sichuan University,
Chengdu 610064, China
1
0 million tons per year [4], which can be typically processed
into valuable consumer products in cosmetics, bulk and fine
Vol:.(1234567890)
1
3

Nonaqueous Biphasic Hydroformylation of Long Chain Alkenes Catalyzed by Water Soluble Phosphine…
439
chemicals industries [5–9]. Rhodium complexes have been
examined as the most effective homogenous catalysts for
hydroformylation as they display high activity and selectiv-
SO3Na
SO3Na
NaO3S
NaO3S
P
P
SO Na
ity under milder reaction conditions [10]. However, a serious
shortcoming of homogeneous catalysis is the cumbersome
separation by distillation of reaction products from catalyst.
Aqueous media are now viewed as excellent means to effect
nearly complete catalyst separation and recovery [11–16], but
3
NaO3S
SO Na
3
SO Na
3
SO3Na
the poor solubility of long chain alkenes (>C ) in water is of
TPPTS
Fig. 1 Structure of TPPTS and BISBIS
BISBIS
6
potential limitation. In addition, this process is not suitable for
water-sensitive substrates.
Recently, as a nontoxic, biodegradable and inexpensive sol-
vent of low volatility, polyethylene glycol (PEG) has attracted
much interest as a recycling solvent [17, 18].
The content of rhodium in products mixture was detected by
inductively coupled plasma-atomic emission spectroscopy
(ICP-AES).
Among rhodium catalyzed hydroformylation of long chain
alkenes in PEG, the tested catalysts are commonly rhodium
complexes with phosphines containing PEG chain or rhodium
polyethylene glycolate complex, so as to increase the solubility
and affinity of the catalyst to PEG. Results obtained show that
the regioselectivity for linear aldehyde is low, alongside, the
rhodium leaching into product phase is high (up to 10 wt% of
the initial amount). To the best of our knowledge, the hydro-
formylation of long chain alkenes catalyzed by rhodium cata-
lyst with water soluble phosphine BISBIS or TPPTS (TPPTS:
sodium salt of sulfonated triphenylphosphine, BISBIS: sodium
salt of sulfonated 2,2′-bis(diphenylphosphinomethyl)-1,1′-
biphenyl) in PEG has not been described yet.
2.2 Hydroformylation and Catalyst Recycling
All hydroformylation was carried out in a 60 mL stainless
steel autoclave equipped with a magnetic stirrer. HRh(CO)
(TPPTS) , TPPTS or BISBIS, PEG and long chain alkene
3
were introduced to the autoclave under a nitrogen atmos-
phere. The autoclave was closed, flushed with syngas three
times, and then pressurized with syngas (H :CO=1:1) to
2
desired pressure and heated to needed temperature for a speci-
fied time. After the reaction was finished, the autoclave was
cooled to room temperature and carefully depressurized. The
product phase was separated from the PEG phase containing
water soluble rhodium catalyst by simple phase separation.
The products were analyzed by GC (PANNA A91, KB-1,
Herein, water soluble phosphine rhodium catalyzed the
hydroformylation of long chain alkenes in PEG (Scheme 1) is
chosen to investigate the reaction performance, phase behavior
and catalyst recycling.
3
0 m×0.25 mm×0.50 µm, FID). In catalyst recycling experi-
2
Experimental
ments, the PEG phase and new portion of long chain alkene
were introduced to the autoclave under a nitrogen atmos-
phere. The other operations were the same as the former
hydroformylation.
2.1 Materials
Ligands TPPTS, BISBIS (Fig. 1) and rhodium precursor
HRh(CO)(TPPTS) were prepared according to literatures [19,
3 Results and Discussion
3
2
0]; DEG (Diethylene glycol), PEG-200, PEG-400 and PEG-
6
00 (the number refers to the average molecular weight) were
As well known, bidentate phosphine ligands are crucial for
regioselectivity control toward linear aldehyde, because their
specific bite angle can improve the regioselectivity [21, 22].
In this report, 1-dodecene was chosen as a probe substrate,
BISBIS as a water soluble bidentate phosphine ligand to
investigate the reaction performance in PEG. Based on our
previous research on rhodium catalyzed hydroformylation
with BISBIS [23, 24], 3.0 MPa of syngas and 120 °C were
purchased from Kelong Chemical Co. of Chengdu. All chemi-
cals were used without any additional purification; 1-octene,
1
-decene and 1-dodecene were purchased from Sigma-Aldrich;
hydrogen (H , 99.99%) and carbon monoxide (CO, 99.9%)
2
were obtained from Southwest Institute. The composition of
reaction mixture was determined by means of gas chromatog-
raphy (PANNA A91, KB-1: 30 m×0.25 mm×0.50 µm, FID).
Scheme 1 Hydroformylation of
O
HRh(CO)(TPPTS) /BISBIS
3
O
H
long chain alkenes
or TPPTS
+
CO + H2
+
R
R
H
PEG
R
linear aldehyde
branched aldehyde
1
3

440
Y. Zhao et al.
selected as reaction parameters. According to the mechanism
in literature [25], the catalytically active specie HRh(CO)(BIS-
BIS) is formed in situ by the ligand exchange reaction between
volume of PEG-200, however, when it further increased, the
1-dodecene conversion dropped to 85.5% due to the decrease
in concentration of rhodium in PEG-200. The optimum dos-
age of PEG-200 was 4.0 mL under the reaction conditions.
It can be seen from Table 1 that the selectivity for aldehydes
achieved 90.0%, accompanied by about 10.0% isomerized
dodecenes and dodecane as the main byproducts and the regi-
oselectivity for linear aldehyde around 95.0%. These results
were similar to that obtained in aqueous biphasic 1-dodecene
hydroformylation catalyzed by Rh/BISBIS in the presence of
a surfactant [24].
HRh(CO)(TPPTS) and BISBIS. The side reactions include
3
isomerization and hydrogenation of 1-dodecene. Table 1 indi-
cates that the average molecular weight of PEG and the vol-
ume of PEG-200 have a significant influence on 1-dodecene
hydroformylation. The conversion of 1-dodecene increased
significantly with the decrease in the average molecular
weight of PEG. The order of 1-dodecene conversion is PEG-
2
00>DEG>PEG-400>PEG-600. Although the solubility of
-dodecene in different PEGs increases with the increase in the
1
Encouraged by the catalytic performance of the above
studied system, the hydroformylation of other long chain
alkenes catalyzed by water soluble phosphine rhodium cata-
average molecular weight of PEG at 120 °C (0.7 g/100 g PEG-
2
00, 3.5 g/100 g PEG-400, 5.9 g/100 g PEG-600), the solubil-
ity of catalyst precursor HRh(CO)(TPPTS) and ligand BIS-
lyst HRh(CO)(TPPTS) and BISBIS in PEG-200 was also
3
3
BIS decreases greatly. For example, the solubility of HRh(CO)
investigated. Results presented in Fig. 2 indicate that the
conversion of long chain alkenes decreased slightly with
increase in carbon number of them. For example, the con-
version of 1-octene was 97.6%, but that of 1-dodecene was
95.1%. The reason might be attributed to the different reac-
tion activity of long chain alkenes. After hydroformylation
finished, the interphase boundary of two phases was very
obvious. The upper phase was colorless, while the lower
phase containing catalyst and BISBIS was golden yellow
(see Fig. 3). Results in Fig. 2 further show that the hydrofor-
mylation of other long chain alkenes was also successfully
performed in PEG-200.
(
TPPTS) in PEG-200 is about 130 g/100 g PEG-200 at 120 °C
3
while the solubility of that in PEG-400 and PEG-600 is only
0
.8 g/100 g PEG-400 and 0.6 g/100 g PEG-600, which results
into much lower conversions of 1-dodecene in PEG-400 and
in PEG-600. 1-dodecene conversion could reach above 95.0%
(
entry 2) after a short reaction time (15 min) in PEG-200. As
the similar explanation in literature [26], the reason may be
that catalyst precursor HRh(CO)(TPPTS) , ligand BISBIS and
3
1
-dodecene have a good solubility in PEG-200 under the reac-
tion conditions. However, the conversion is only 0.8% when
water was used as a solvent in 1-dodecene hydroformylation
due to the much lower solubility of 1-dodecene in water. In
tested experiments, the regioselectivity for linear aldehyde
remained almost about 95.0%, which is attributed to the biden-
tate ligand BISBIS with e.e. Configuration [27]. Results in
Table 1 also show that the volume of PEG-200 has a obvious
effect on activity of 1-dodecene hydroformylation. The rate of
Table 2 firstly summarizes the recycling experimental
results in 1-dodecene hydroformylation catalyzed by the
catalytic system derived from HRh(CO)(TPPTS) , BISBIS
3
and PEG-200, exhibiting high catalytic efficiency and long
service life with no significant loss in activity, selectivity
or Rh loss for more than five cycles. TPPTS is one of the
most widely used water soluble monodentate phosphines,
1-dodecene hydroformylation increased with increasing the
Table 1 Hydroformylation of
-dodecene with HRh(CO)
TPPTS) /BISBIS system in
Conv. (%)a
SAld. (%)b
SLinear ald. (%)c
−1 d
Entry
Solvent
Volume (mL)
TOF (h
)
1
(
3
1
2
3
4
5
6
7
8
9
DEG
4.0
4.0
4.0
4.0
4.0
1.0
2.0
4.0
5.0
78.2
95.1
25.3
1.7
89.4
90.1
88.6
53.8
89.8
90.6
91.0
90.1
88.3
96.9
96.5
95.8
98.2
93.8
96.8
96.7
96.5
96.4
1408
1712
455
31
14
1136
1604
1712
1539
PEG
PEG-200
PEG-400
PEG-600
H O
0.8
2
PEG-200
PEG-200
PEG-200
PEG-200
63.1
89.1
95.1
85.5
Reaction conditions Rh=2.0×10− mmol, [BISBIS]/[Rh]=17.5, S/C=450, 1-dodecene=2.0 mL,
2
P=3.0 MPa (CO:H =1.0:1.0), T=120 °C, t=15 min
2
a
Conversion of 1-dodecene
Selectivity for aldehydes
Linear aldehyde content in total aldehydes
Turnover frequency defined as the moles of converted alkene per mole of Rh per hour
b
c
d
1
3

Nonaqueous Biphasic Hydroformylation of Long Chain Alkenes Catalyzed by Water Soluble Phosphine…
441
however, the activity decreased slightly after five catalytic
cycles when BISBIS was replaced with TPPTS. The main
reason may be that TPPTS was partly oxidized owing to
contact with air during the separation. In contrast, the chelat-
ing complex Rh/BISBIS formed with HRh(CO)(TPPTS)
3
and bidentate ligand BISBIS is more stable during the
separation. Therefore the catalyst recycling is significantly
improved. As far as the two catalytic systems, the content of
rhodium leaching into product phase was less than 0.06 wt%
because of their own strong charge of BISBIS and TPPTS.
It could be seen that the catalytic systems consisting of
HRh(CO)(TPPTS) , TPPTS or BISBIS and PEG-200 show
3
a good catalyst recycling performance.
4
Conclusions
Fig. 2 Hydroformylation of long chain alkenes with HRh(CO)
TPPTS) /BISBIS in PEG-200 Reaction conditions: Long chain alk-
(
3
In conclusion, a simple, highly effective and recyclable
hydroformylation catalytic system for long chain alkenes has
been established based on water soluble phosphine BISBIS
ene=2.0 mL, PEG-200=4.0 mL, others are the same as in Table 1
or TPPTS, HRh(CO)(TPPTS) and PEG-200, which showed
3
an excellent hydroformylation efficiency for 1-octene,
1
-decene and 1-dodecene. The analysis of Rh loss and cata-
lyst recycling experiments indicated that the water soluble
phosphine rhodium catalysts can be effectively immobilized
in PEG-200 due to the strong charge of BISBIS or TPPTS,
which significantly improved the stability and reusability of
catalytic system during the catalytic cycle. No significant
loss of catalytic efficiency or Rh was observed for more than
five cycles. Nowadays, the application of the catalytic sys-
tems in functional olefin hydroformylation and other reac-
tions was under the way.
before reaction
after reaction
Acknowledgements We thank the financial support from the Sichuan
university outstanding scholar research fund (No. 2015SCU04A05), the
National Natural Science Foundation of China (No. 201202108), and
the Opening Project of Key Laboratory of Green Chemistry of Sichuan
Institutes of Higher Education (No. LZJ1402).
Fig. 3 Picture of before and after reaction
Table 2 Catalyst recycling with HRh(CO)(TPPTS) /BISBIS or
3
TPPTS in PEG-200
Conv. (%) SAld. (%) SLinear ald. (%) TOF(h−1
)
References
Run Ligand
1
2
3
4
5
1
2
3
4
5
BISBIS 93.8
89.6
91.5
91.8
92.1
90.9
92.9
91.7
90.0
90.1
89.9
96.2
95.0
94.7
94.4
94.4
73.3
74.3
74.3
75.8
75.9
1688
1699
1714
1694
1696
1784
1760
1688
1636
1449
1
2
.
.
Agbossou F, Carpentier JF, Mortreux A (1995) Asymmetric
hydroformylation. Chem Rev 95:2485
94.4
95.2
94.1
Brezny AC, Landis CR (2017) Unexpected CO dependencies,
catalyst speciation, and single turnover hydrogenolysis studies
of hydroformylation via high pressure NMR spectroscopy. J Am
Chem Soc 139:2778
94.2
TPPTS 99.1
97.8
3. van Leeuwen PWNM, Claver C (eds) (2000) Rhodium catalyzed
hydroformylation. Kluwer Academic Publishers, Dordrecht
4
.
Franke R, Selent D, Börner A (2012) Applied hydroformylation.
Chem Rev 112:5675
93.8
90.9
80.5
5
.
Wang YY, Chen JH, Luo MM, Chen H, Li XJ (2006) Highly regi-
oselective hydroaminomethylation of long chain alkenes catalyzed
by Rh-BISB6IS in a two-phase system. Catal Commun 7:979
Reaction conditions 1-dodecene=2.0 mL, [P]/[Rh]=35.0, PEG-
00=4.0 mL, others are the same as in Table 1
6. Eilbracht P, Bärfacker L, Buss C, Hollmann C, Kitsos-Rzychon
BE, Kranemann CL, Rische T, Roggenbuck R, Schmidt A (1999)
2
1
3

442
Y. Zhao et al.
Tandem reaction sequences under hydroformylation conditions:
new synthetic applications of transition metal catalysis. Chem Rev
18. Borrmann T, Roesky HW, Ritter U (2000) Biphasic hydroformyla-
tion of olefins using a novel water soluble rhodium polyethylene
glycolate catalyst. J Mol Catal A 153:31
9
9:3329
7
.
.
Liu Y, Li ZH, Wang B, Zhang Y (2016) A fine dispersed cobalt
catalyst with macro-pore for hydroformylation of 1-hexene. Catal
Lett 146:2252
19. Herrmann WA, Kohlpaintner CW, Bahrmann H, Knokol W (1992)
Water-soluble metal complexes and catalysts Part 6. A new, effi-
cient water-soluble catalyst for two-phase hydroformylation of
olelins. J Mol Catal 73:191
8
9
Jin X, Zhao K, Kong FF, Cui FF, Liu QQ, Zhang YW (2014) The
mechanism of acetal formation in acid-free Rh-catalyzed tandem
hydroformylation-acetalization of olefins in MeOH. Catal Lett
20. Chen H, Liu HC, Li YZ, Cheng FM, Li XJ (1994) J Mol Catal
8:124
1
44:192
21. Kamer PCJ, vanLeeuwen PWNM., Reek JNH (2001) Wide bite
angle diphosphines: xantphos ligands in transition metal com-
plexes and catalysis. Acc Chem Res 34:895
.
Zhang L, Li C, Zheng XL, Fu HY, Chen H, Li RX (2014) Synthe-
sis, characterization of N-pyrrolylphosphanes based on heterocy-
clic amine backbones and their application in hydroformylation
of 1-octene. Catal Lett 144:1074
22. van Leeuwen PWNM., Kamer PCJ, Reek JNH, Dierkes P (2000)
Ligand bite angle effects in metal-catalyzed C–C bond formation.
Chem Rev 100:2741
1
1
1
1
0. Behr A, Neubert P (2013) Applied homogeneous catalysis. Angew
Chem Int Ed 52:1627
23. Yuan ML, Chen H, Li RX, Li YZ, Li XJ (2004) High active and
regioselective hydroformylation of 1-dodecene catalyzed by Rh-
BISBIS in a two-phase system. Cat Lett 94:15
1. Kuntz EG (1987) Homogeneous catalysis in water. Chem Tech
1
7:570
2. Cornils B, Wiebus E (1995) Aqueous catalysts for organic reac-
tions. Chem Tech 23:33
24. Yuan ML, Chen H, Li RX, Li YZ, Li XJ (2003) Hydroformylation
of 1-butene catalyzed by water-soluble Rh–BISBIS complex in
aqueous two-phase catalytic system. Appl Cat A 251:181
25. Walter S, Spohr H, Franke R, Hieringer W, Wasserscheid P,
Haumann M (2017) Detailed investigation of the mechanism of
Rh-Diphosphite supported ionic liquid phase (SILP)-catalyzed
1-butene hydroformylation in the gas phase via combined kinetic
and density functional theory (DFT) modeling studies. ACS Catal
7:1035
3. Cornils B, Kuntz EG (1995) Introducing TPPTS and related
ligands for industrial biphasic processes. J Organomet Chem
5
02:177
1
1
1
4. Cornils B, Herrmann WA, Eckl RW (1997) Industrial aspects of
aqueous catalysis. J Mol Catal A 116:27
5. Cornils B (1999) Bulk and fine chemicals via aqueous biphasic
catalysis. J Mol Catal A 143:1
6. Siangwata S, Baartzes N, Makhubela BCE, Smith GS (2015) Syn-
thesis, characterisation and reactivity of water-soluble ferroce-
nylimine-Rh(I) complexes as aqueous-biphasic hydroformylation
catalyst precursors. J Organomet Chem 796:26
26. Fu HY, Li M, Chen J, Zhang RM, Jiang WD, Yuan ML, Chen H,
Li XJ (2008) Application of a new amphiphilic phosphine in the
aqueous biphasic catalytic hydroformylation of long chain olefins.
J Mol Catal A: Chem 292:21
1
7. Feng CL, Wang YH, Jiang JY, Yang YC, Yu FL, Jin ZL (2006)
Using thermoregulated PEG biphase system to effect the hydrofor-
mylation of p-isobutylstyrene catalyzed by Rh/OPGPP complex.
J Mol Catal A 248:159
27. Casey CP, Whiteker GT, Melville MG, Petrovich LM, Gavney JA
Jr, Powell DR (1992) Diphosphines with natural bite angles near
120° increase selectivity for n-aldehyde formation in rhodium-
catalyzed hydroformylation. J Am Chem Soc 114:5535
1
3