Tandem Hydroformylation–Acetalization Using a Water-Soluble Catalytic System: a Promising Procedure for Preparing Valuable Oxygen-Containing Compounds from Olefins and Polyols

Article abstract of DOI:10.1134/S1070427218060174

Specific features of the tandem hydroformylation–acetalization of a series of unsaturated compounds and polyols in the presence of a water-soluble catalytic system containing a rhodium catalyst precursor, sodium (triphenylphosphino)trisulfonate, and H₂SO₄ were investigated. The process parameters, including component ratio, temperature, and reaction time, were optimized using model substrates. With the suggested catalytic system, the conversion of unsaturated compounds to target products, acetals, reached 95%, and the catalytic system could be separated from the reaction products and repeatedly used without considerable loss of the activity. The acetal preparation procedure is versatile with respect to the raw materials. Batches of acetal mixtures were prepared by the suggested procedure from 1-octene and polyols, e.g., ethylene glycol, glycerol, and sorbitol.

Full text of DOI:10.1134/S1070427218060174

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2018, Vol. 91, No. 6, pp. 990−995. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © D.N. Gorbunov, M.V. Nenasheva, N.A. Sinikova, Yu.S. Kardasheva, A.L. Maksimov, E.A. Karakhanov, 2018, published in Zhurnal
Prikladnoi Khimii, 2018, Vol. 91, No. 6, pp. 859−865.
ORGANIC SYNTHESIS AND INDUSTRIAL
ORGANIC CHEMISTRY
Tandem Hydroformylation–Acetalization Using a Water-Soluble
Catalytic System: a Promising Procedure for Preparing Valuable
Oxygen-Containing Compounds from Olefins and Polyols
D. N. Gorbunova, M. V. Nenashevaa, N. A. Sinikovaa, Yu. S. Kardashevaa,
A. L. Maksimovb, and E. A. Karakhanova,*
a Moscow State University, Moscow, 119991 Russia
b Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia
e-mail: suskab_91@mail.ru
Received May 28, 2018
Abstract—Specific features of the tandem hydroformylation–acetalization of a series of unsaturated compounds
and polyols in the presence of a water-soluble catalytic system containing a rhodium catalyst precursor, sodium
(triphenylphosphino)trisulfonate, and sulfuric acid were studied. The process parameters (component ratio,
temperature, reaction time) were optimized using model substrates. With the suggested catalytic system, the
conversion of unsaturated compounds to target products, acetals, reaches 95%, and the catalytic system can
be separated from the reaction products and repeatedly used without significant loss of the activity. The acetal
preparation procedure is versatile with respect to the raw materials. Batches of acetal mixtures were prepared by
the suggested procedure from 1-octene and polyols (ethylene glycol, glycerol, sorbitol).
DOI: 10.1134/S1070427218060174
The mankind’s desire for economical and environ-
mentally friendly consumption of natural resources
makes it topical to develop technologies for deep pro-
cessing of hydrocarbon raw materials and various
wastes. Polyols are wastes from the production of sug-
ars and biodiesel. These hydrophilic oxygen-containing
wastes do not always find proper application, and on the
glycerol market the supply exceeds the demand because
of rapid development of the biodiesel production [1, 2].
Therefore, problems of reprocessing polyols become
very topical.
agrochemical formulations, e.g., to those containing
herbicides, insecticides, fungicides, or plant growth
stimulants, improves the retention of active substances
on the surface and their subsequent penetration into
plant leaves [6]. It seems promising to use acetals as
additives to hydrocarbon fuels for internal combustion
engines, namely, to gasolines and diesel fuels. Acetals
can be used for increasing the octane number of
gasolines [7] or improving the properties of biodiesel
(viscosity, oxidation resistance, flash point, etc.), or as
antifreezes for biodiesel [8–10]. Addition of acetals to
gas oil or diesel fuel decreases the emission of harmful
substances, in particular, as solid particles [11]. Addition
of 1,3-dioxolanes to lubricating oils and fuels enhances
their oxidation resistance, improves the fuel purity, and
decreases the friction and fuel consumption [12].
One of the ways of reprocessing polyols involves
their hydrophobization by reactions with carbonyl
compounds to obtain cyclic acetals and ketals.
Compounds of these classes can be used as solvents,
detergents, emulsifiers, components of cosmetics, and
technical additives, e.g., to lubricants and hydraulic
oils [3, 4], and also as fragrances [5]. Acetals derived
from polyols show promise in agricultural chemistry
owing to their ability to considerably reduce the surface
tension without foaming. Therefore, their addition to
Classical procedures for preparing cyclic acetals
consist in performing acetalization on acid catalysts with
azeotropic distillation of water [13]. These procedures
required the use of expensive aldehydes as raw materials
and of high-performance, preferably heterogeneous,
990

TANDEM HYDROFORMYLATION–ACETALIZATION
Products of large-tonnage chemistry Fine organic synthesis
991
Ethylene
Propylene
Linear olefins С5–С14
Propylene trimers
Butylene dimers
Fischer–Tropsch synthesis products
Styrene
Pinenes
Terpenes
Norbornene
Cycloalkenes
Dienes
Fig. 1. Versatility of the suggested procedure for preparing acetals with respect to the raw material.
catalysts; therefore, they are hardly promising for
commercial implementation.
from long-chain olefins and polyols of complex struc-
ture (xylitol, sorbitol) by hydroformylation–acetaliza-
tion [14]; some previously unknown compounds were
synthesized and characterized. In our study, we used
(acetylacetonato)dicarbonylrhodium Rh(acac)(CO)2 as
a catalytic precursor for hydroformylation. High cata-
lytic activity of rhodium compounds ensures the pos-
sibility of performing the processes at pressures of up to
8.0 MPa, which is considerably lower than the pressures
used in cobalt-catalyzed hydroformylation (≥23.0 MPa).
However, because of high cost of rhodium, it is topical
to search for the ways to stabilize, separate, and repeat-
edly use rhodium catalysts.
This study deals with the synthesis of cyclic acetals
by tandem hydroformylation–acetalization directly from
unsaturated raw materials from oil refining processes,
without isolation and purification of the intermediate
aldehydes. Thus, the study is aimed at expanding
the application sphere of the available resources and
at developing an efficient procedure for preparing a
promising class of oxygen-containing compounds.
RESULTS AND DISCUSSION
The Poulenc–Ruhrchemie process is one of the
most attractive processes for the catalyst separation.
It is performed under the conditions of phase-transfer
catalysis using a water-soluble phosphine ligand,
TPPTS [sodium (triphenylphosphino)trisulfonate] [22].
Previously our team [14, 15] and other research teams
[16–21] examined the possibility of preparing various
cyclic acetals by tandem hydroformylation–acetaliza-
tion under homogeneous conditions in organic solvents.
Novel procedures were suggested for preparing acetals
Fig. 2. Scheme of the hydroformylation–acetalization tandem reaction with 1-octene and ethylene glycol as examples.
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992
GORBUNOV et al.
Table 1. Hydroformylation–acetalization parameters
Optimization of conditions of catalytic experi-
ments. Initially we optimized the conditions of the
tandem process. The important parameters that require
optimization and influence not only the conversion but
also the power and resource consumption are the reac-
tant ratio and temperature. The optimum reaction condi-
tions were found using model substrates, 1-octene and
ethylene glycol (Fig. 2).
Parametera
Value
Molar ratio S1/Rh
Molar ratio L/Rh
Molar ratio S2/S1
1000:1–10000:1
3 : 1–10 : 1
1.2 : 1–3 : 1
0.2 : 1–1 : 1
Weight ratio of aqueous
and organic phases
The optimum conditions of catalytic experiments,
ensuring high 1-octene conversion (>90%) and high
selectivity with respect to acetals (>70%), are given in
Table 1.
Acid content, wt %
Temperature, °C
0.5–3
70–110
4.0–8.0
CO/H2 (1 : 1) pressure,
MPa
Our next task was to expand the range of substrates
and to scale the synthesis to obtain pilot batches of
acetals.
Reaction time, h
4–8
The unsaturated substrates (terminal linear С6–С14
olefins and propylene trimers) and polyols were varied,
and the parameters indicated in Table 1 were kept con-
stant. The total yield of the acetals is given in Table 2.
a L is phosphine ligand TPPTS, S1 is the unsaturated substrate,
and S2 is the polyol.
As shown by the examples of hydroformylation–ac-
etalization of 1-octene in the presence of ethylene gly-
col, glycerol, and sorbitol, recirculation of the catalytic
system is possible without significant loss in its activity
(Fig. 3).
In this study, the Poulenc-Ruhrchemie process was
taken as a basis for the development of processes for
synthesizing cyclic acetals. The possibility of preparing
acetals under the phase-transfer conditions is due to
different polarity of the catalytic system components
and reaction products. The starting polyol, sulfuric acid,
and the catalyst occur in the aqueous phase, whereas the
formed reaction products are extracted into the organic
phase.
Thus, we have demonstrated the possibility of
preparing ~500-mL batches of acetals for further studies
of their consumer properties.
Scaling of the experiment and production of pilot
batches of the acetals. The batches were produced in a
1-L high-pressure steel reactor equipped with a power-
driven stirrer and a temperature-control device. The
olefin was loaded in an amount of 100 mL and more.
After the reaction completion, reactor cooling, and
Because of the diversity of the starting reactants
and versatility of the suggested method, it is possible
to prepare a wide range of products, acetals of various
structures, both as large-tonnage products and as
products of fine chemical synthesis (Fig. 1).
Ethylene glycol
Glycerol
Sorbitol
Number of repeated experiments
Fig. 3. Recirculation of the catalytic system. Conditions: Rh(acac)(CO)2 (3 mg, 0.011 mmol), TPPTS (34.8 mg, 6 mmol), 1 M aqueous
H2SO4 (0.6 mL), olefin (7.6 mmol), polyol (10.0 mmol), 80°С, p(CO/H2, 1 : 1 ) = 4.0 MPa, 5 h.
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TANDEM HYDROFORMYLATION–ACETALIZATION
993
Table 2. Preparation of acetals from various substrates by hydroformylation–acetalization. Conditions: Rh(acac)(CO)2 (3 mg,
0.011 mmol), TPPTS (34.8 mg, 6 mmol), 1 M aqueous H2SO4 solution (0.6 mL), olefin (7.6 mmol), polyol (10.0 mmol), 80°С,
p(CO/H2, 1 : 1) = 4.0 MPa, 5 h
Unsaturated substrate
С6
С8
С10
С12
С14
Polyol
propylene trimers
yield of acetals,a %
Ethylene glycol
Glycerol
94
89
80
65
92
87
79
60
92
85
76
58
90
80
74
55
84
76
70
54
42
Pentaerythritol
Sorbitol
No tests
a
The yield of acetals was determined as the product of the unsaturated substrate conversion (%) and the percentage of acetals in the final
mixture, determined by GLC.
Table 3. Batches of samples of acetal mixtures
Sample Substrate
Sample composition and content of components
G1-FA
1-Octene
Ethylene glycol
G2-FA
1-Octene
Glycerol
G3-FA
1-Octene
Sorbitol
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GORBUNOV et al.
Table 4. Production of batches of acetal mixtures.a Conditions: Rh(acac)(CO)2 (150 mg, 0.58 mmol), TPPTS (2 g, 3.5 mmol),
1 M aqueous H2SO4 solution (40 mL), olefin (0.65 mol), polyol (0.8 mol), 80°С, p(CO/H2, 1 : 1 ) = 6.0 MPa, 8 h
Number of
recycles, total
synthesis time
Weight of the
acetals obtained,
g
Weight of the loaded
1-octene, g
Total yield of
acetals, %
Substrate
TOF, h–1
Ethylene glycol
Glycerol
5 recycles, 40 h
350
350
350
490
525
430
85
75
60
197
168
134
Sorbitol
a Five repeated experiments on production of acetals for each substrate.
discharge of the gases, we took off the organic phase
containing the reaction products (acetals), unchanged
olefins, and intermediates (aldehydes). A fresh portion
of the polyol was added to the aqueous phase, and after
adding a new portion of the olefin in an organic solvent
the aqueous phase was reused. The organic phases
after a series of repeated syntheses were combined and
subjected to fractional vacuum distillation to separate the
acetal fraction from the solvent, olefins, and aldehydes.
The composition of the acetal fractions was monitored
by gas–liquid chromatography and NMR spectroscopy.
By the above-described procedure, we prepared acetal
mixture samples G1-FA, G2-FA, and G3-FA. Their
composition is given in Table 3. The mixtures were not
separated into individual components.
of the mixtures by gas–liquid chromatography was
performed with a Hewlett–Packard chromatograph
equipped with a flame ionization detector and a
30-m-long capillary column coated with SE-30 under
the conditions of programmed heating from 60 to 230°С.
The carrier gas was helium. The analysis was performed
in the presence of n-nonane as internal reference.
Procedure for preparing acetals under the
conditions of phase-transfer catalysis. The reactions
were performed in a 50-mL steel autoclave equipped
with a magnetic stirrer and a temperature-control device
at temperatures of up to 100°С. The autoclave was
charged with the solvent (toluene, 1 mL), components
of the water-soluble catalytic system [Rh(acac)(CO)2
(3 mg, 0.011 mmol), TPPTS (34.8 mg, 6 mmol)], 1 M
aqueous H2SO4 (0.6 mL), and the substrates: olefin
(7.6 mmol) and polyol (10.0 mmol). The autoclave was
purged with syngas, filled with syngas (CO : H2 = 1 :
1) to a pressure of 4.0 MPa, and heated for 5 h at 80°C
with continuous stirring. After the reaction completion,
the autoclave was cooled to room temperature. The
products were analyzed by GLC (with the addition of
n-nonane as internal reference, 0.6 mL, 3.8 mmol) and
by 1Н and 13С NMR spectroscopy.
To evaluate the processes, we determined the total
acetal yields and the turnover frequency (TOF) of the
catalytic system (Table 4).
The TOF value obtained appeared to be relatively
low. This is caused by the chosen initial olefin/Rh molar
ratio and by the long reaction time. Further optimization
involves studying the reaction kinetics and determining
the reaction time and the substrate/catalyst ratio ensuring
the maximal TOF values.
Production of pilot batches of acetal mixtures.
The reactions were performed in a 1-L steel autoclave
equipped with a power-driven stirrer and a temperature-
control device operating at temperatures of up to 300°С.
The autoclave was charged with the organic solvent
(toluene, 30 mL), components of the water-soluble
catalytic system [Rh(acac)(CO)2 (150 mg, 0.58 mmol),
TPPTS (2 g, 3.5 mmol)], 1 M aqueous H2SO4 (40
mL), and the substrates: olefin (0.65 mol) and polyol
(0.8 mol). The autoclave was purged with syngas, filled
with syngas (CO : H2 = 1 : 1) to a pressure of 6.0 MPa,
and heated for 8 h at 80°C with continuous stirring.
After the reaction completion, the autoclave was cooled
EXPERIMENTAL
1-Hexene, 1-octene, 1-decene, 1-dodecene, ethylene
glycol, glycerol, pentaerythritol, xylitol, sorbitol,
and TPPTS (Sigma–Aldrich) were used without any
pretreatment. Propylene trimers (98% olefins) were
placed at our disposal by Tatneftekhiminvest Holding.
The solvents were pretreated by standard procedures.
(Acetylacetonato)dicarbonylrhodium Rh(acac)(CO)2
was prepared by the known procedure [23].
The H and 13C NMR spectra were recorded on a
Varian XL-400 device operating at 400 MHz. Analysis
1
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TANDEM HYDROFORMYLATION–ACETALIZATION
995
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to room temperature, the pressure was relieved, and
the organic phase was unloaded. The organic phase
1
composition was determined by GLC and by Н and
13С NMR. A new portion of the polyol (80% of the
previous loading), unsaturated substrate (0.65 mol),
and toluene (30 mL) were added to the aqueous phase
remaining in the autoclave. The combined organic
phases were subjected to fractional vacuum distillation
to separate the unchanged olefins, aldehydes, and
toluene and obtain a mixture of acetals. Their purity was
checked by GLC and by NMR spectroscopy.
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13. Climent, M.J., Corma, A., and Iborra, S., Green Chem.,
A procedure was suggested for preparing acetals
of various compositions and their mixtures by tandem
hydroformylation–acetalization using a water-soluble
catalytic system. The yield of cyclic acetals is 50–95%
depending on the kind of the raw material; i.e., the
procedureisversatile.Thecatalyticwater-solublesystem
can be readily separated from the reaction products; it
does not lose the catalytic activity in repeated use. The
optimum reaction conditions were determined. Under
these conditions, the experiments were performed to
produce pilot batches of acetal samples from 1-octene
and polyols: ethylene glycol, glycerol, and sorbitol. The
performance of the catalytic system, evaluated by TOF,
was about 200 h–1, and the time of stable operation of
the catalytic system exceeded 40 h.
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