Hydroalkoxycarbonylation of isobutylene with polyhydric alcohols in the presence of catalytic systems based on palladium compounds and tertiary phosphines

Article abstract of DOI:10.1134/S0965544112030127

The reaction of isobutylene hydroalkoxycarbonylation at low carbon monoxide pressures (≤2.0 MPa) with ethylene glycol and glycerol in the presence of catalytic systems based on Pd and mono- and bidentate organic phosphines has been studied. The effect of different conditions of the reaction in the presence of the Pd(Acac)₂-PPh₃-TsOH catalyst system on the ratio of the products, mono- and diglycolides (mono-, di-and triglycerides) of isovaleric acid has been investigated. The relative catalytic activity of a number of binary and ternary systems based on synthesized Pd(Acac)₂, Pd(PPh₃)₄, and PdCl₂(PPH₃) ₂ complexes has been determined. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S0965544112030127

ISSN 0965ꢀ5441, Petroleum Chemistry, 2012, Vol. 52, No. 3, pp. 189–193. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © Kh.A. Suerbaev, E.G. Chepaikin, N.O. Appazov, B.Zh. Dzhiembaev, 2012, published in Neftekhimiya, 2012, Vol. 52, No. 3, pp. 215–219.
Hydroalkoxycarbonylation of Isobutylene with Polyhydric Alcohols
in the Presence of Catalytic Systems Based on Palladium Compounds
and Tertiary Phosphines
Kh. A. Suerbaeva, E. G. Chepaikinb, N. O. Appazova, and B. Zh. Dzhiembaeva
a AlꢀFarabi Kazakh National University, ul. AlꢀFarabi 71, Almaty, 050038 Kazakhstan
b Institute of Structural Macrokinetics and Materials Science, Russian Academy of Sciences, Chernogolovka, 142432 Russia
eꢀmail: echep@ism.ac.ru; grig@ism.ac.ru
Received December 9, 2010
Abstract—The reaction of isobutylene hydroalkoxycarbonylation at low carbon monoxide pressures
( 2.0 MPa) with ethylene glycol and glycerol in the presence of catalytic systems based on Pd and monoꢀ and
≤
bidentate organic phosphines has been studied. The effect of different conditions of the reaction in the presꢀ
ence of the Pd(Acac)2–PPh3–TsOH catalyst system on the ratio of the products, monoꢀ and diglycolides
(monoꢀ, diꢀand triglycerides) of isovaleric acid has been investigated. The relative catalytic activity of a numꢀ
ber of binary and ternary systems based on synthesized Pd(Acac)2, Pd(PPh3)4, and PdCl2(PPH3)2 complexes
has been determined.
DOI: 10.1134/S0965544112030127
Hydroalkoxycarbonylation of isobutylene with carꢀ
bon monoxide and alcohols under conditions of
homogeneous catalysis by transition metal complexes
is an efficient method for the synthesis of isovaleric
acid esters, which find wide practical application.
EXPERIMENTAL
The coordination complexes PdCl2(PPh3)2,
Pd(Acac)2, and Pd(PPh3)4 and the ligands PPh3,
Ph2PCH2PPh2, and Ph2PCH2CH2PPh2 were obtained
according to the procedures described in [7–10].
Commercial reagentꢀgrade ethylene glycol and glycꢀ
Note that the hydroalkoxycarbonylation reaction
of olefins with CO and monohydric alcohols has been
widely studied [1]. Of course, the extension of this
method to polyols for obtaining polyol esters of carꢀ
boxylic acids, which are widely used as plasticizers,
components of pharmaceuticals and cosmetics, wetꢀ
ting agents, and emulsifiers, is of practical interest [2].
The esters of polyhydric alcohols are also used in the
manufacture of synthetic lubricants [3].
erol were used without special purification. nꢀTolueꢀ
nesulfonic acid was recrystallized from 96% ethanol
and dried to have the TsOH · H2O composition. The
experiments were carried out in the solventꢀfree mode.
A steel autoclave of 150 mL capacity was charged
with 0.035 g (1.1
8.085
10–4 mol) of PPh3, 0.263 g (1.386
of TsOH, and 3.94 g (6.35
10–2 mol) of ethylene glyꢀ
col or 5.975 g (6.35
10–2 mol) of glycerol. The autoꢀ
× g
10–4 mol) of Pd(Acac)2, 0.212
(
×
×
10–3 mol)
×
There are patent data [2, 4, 5] on the synthesis of
polyol esters of carboxylic acids by the hydroalkoxyꢀ
carbonylation reaction of olefins with carbon monoxꢀ
ide and polyols in the presence of twoꢀcomponent catꢀ
alyst systems consisting of Co, Ni or Rh compounds
(octanoates, stearates, chlorides, or carbonates) and
pyridine (or its derivatives).
×
clave was sealed, purged twice with CO to remove air
from the system, and then filled with CO to a pressure
of 1.0–1.1 MPa. After that, the calculated amount of
isobutylene (one or two equivalents relative to ethylꢀ
ene glycol or one, two, or three equivalents relative to
glycerol) was introduced, and the CO pressure was
We previously showed the feasibility of the syntheꢀ brought to the desired value. After that, stirring and
sis of glycolides (glycerides) of isovaleric acid by the heating were turned on. The reaction mixture was
isobutylene hydroalkoxycarbonylation reaction at low stirred for varying durations of the process at different
CO pressures ( 2.0 MPa) in the presence of ethylene temperatures, reactant ratios, and catalyst component
≤
glycol (glycerol) and the Pd(Acac)2–PPh3–TsOH sysꢀ ratios. Then, the autoclave was cooled to room temꢀ
tem [6]. The aim of this work was to study the effect of perature and left to stay overnight. After releasing the
various reaction conditions on the ratio of the prodꢀ pressure to an atmospheric value, the reaction mixture
ucts monoꢀ and diglycolides (monoꢀ, diꢀ, and triglycꢀ was fractionated in a vacuum (1 mmHg). From the
erides) of isovaleric acid and to determine the catalytic resulting product mixture, the desired products were
activity of other systems based on Pd phosphine comꢀ isolated by column adsorption chromatography on silꢀ
plexes.
ica gel (0.005–0.04 mm) with a 9 : 1 (by volume) chloꢀ
189

190
SUERBAEV et al.
Table 1. Isobutylene hydroalkoxycarbonylation with CO and ethylene glycol in the presence of the Pd(acac)2–PPh3–
TsOH catalytic system. Quantity of loaded Pd(acac)2, 0.035 g (1.1
×
10–4 mol)
Molar ratio of reactants and components
Reaction conditions
Yield of glycolides, wt %
of the catalytic system
Isobutyꢀ Ethylene
No.
Pd(Acac)2 PPh3
TsOH
T
,
°
C
P
CO, atm
τ
, h
Monoꢀ
Diꢀ
Total
lene
glycol
1
2
3
4
5
6
7
8
9
550
550
550
550
550
550
550
550
550
550
550
550
550
550
550
550
550
550
550
550
450
650
550
550
550
550
550
550
550
550
550
550
550
550
183.3
275
825
1100
550
550
550
550
450
650
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
6
8
7
7
7
7
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
11
13
12
12
80
90
20
20
20
20
10
15
25
30
20
20
20
20
20
20
20
20
20
20
20
20
20
20
3
3
3
3
3
3
3
3
1
2
4
5
3
3
3
3
3
3
3
3
3
3
9.9
10.0
25.0
10.7
19.6
31.2
26.0
25.8
0.8
3.1
6.1
13.0
16.1
41.8
16.1
22.9
36.8
35.0
33.9
2.6
100
110
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
16.8
5.4
3.3
5.6
9.0
8.1
1.8
10
2.5
4.7
7.2
11
12
13
14
15
16
17
18
19
20
21
22
16.2
8.1
17.8
7.3
34.0
15.4
26.8
38.0
21.7
14.9
13.1
27.0
12.7
30.7
34.0
4.6
17.4
17.9
17.6
11.0
10.9
11.4
10.5
13.9
24.8
4.5
9.4
20.1
4.1
3.9
2.2
15.6
2.2
16.8
9.2
0.1
roform : methanol solvent blend as the eluent. The give products with the linear structure (isovalerates).
identity of the products was determined by thinꢀlayer Table 1 presents the results of examining the effect of
chromatography, elemental analysis, IR spectroscopy, various reaction conditions on the yield of monoꢀ and
1
and H and 13C NMR techniques. The purity of the diglycolides of isovaleric acid. As is seen, the depenꢀ
products was determined by thin layer chromatograꢀ dences of the product yields on the reaction temperaꢀ
phy on Silufol (Czech Republic) in chloroform or in ture (entries 1–4), CO pressure (entries 3, 5–8), and
the 9 : 1 (by volume) chloroform : methanol solvent the reaction time (entries 3, 9–12) are nonmonotonic
system. The 1H and 13C NMR spectra were taken on a in character. The optimal conditions were as follows:
Bruker DPXꢀ400 instrument.
temperature, 100°С; CO pressure, 2.0 MPa; and reacꢀ
tion time, 3 h. Under these conditions, the total yield
of monoꢀ and diglycolides of isovaleric acid reached
41.8% (Table 1, entry 3).
RESULTS AND DISCUSSION
It was found that isobutylene carbonylation with
The reactants (isobutylene, ethylene glycol) ratio is
CO and ethylene glycol (glycerol) in the presence of of considerable importance (Table 1, entries 3, 13–
the Pd(Acac) –PPh –TsOH system proceeds regioseꢀ 16). The optimal [isobutylene] : [ethylene glycol] ratio
2
3
lectively at the terminal atom of the reactant olefin to was 1 : 1; the increase in the ratio from 1 to 3 reduced
PETROLEUM CHEMISTRY Vol. 52
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2012

HYDROALKOXYCARBONYLATION OF ISOBUTYLENE WITH POLYHYDRIC ALCOHOLS
191
Table 2. Isobutylene hydroalkoxycarbonylation with CO and glycerol in the presence of the Pd(acac)2–PPh3–TsOH catꢀ
alytic system. Quantity of loaded Pd(acac)2, 0.035 g (1.1
×
10–4 mol)
Molar ratio of reactants and components
Reaction conditions
Yield of glycerides, wt %
of the catalytic system
No.
Isobutyꢀ
lene
Pd(Acac) PPh3 TsOH
T
,
°
C
P
CO, atm
τ
, h
Monoꢀ
Diꢀ
Triꢀ
Total
Glycerol
2
1
2
3
4
5
6
7
8
9
1100
1100
1100
1100
1100
1100
1100
550
550
550
550
550
550
550
550
550
550
1
1
1
1
1
1
1
1
1
7
7
7
7
7
7
7
7
7
12
12
12
12
12
12
12
12
12
100
100
100
90
20
20
20
20
20
15
25
20
20
2
3
4
3
3
3
3
3
3
2.5
16.2
11.3
–
13.3
13.1
10.4
10.8
8.8
–
–
15.8
29.3
21.7
14.6
15.9
14.8
13.9
13.1
22.9
–
3.8
–
110
100
100
100
100
7.1
–
9.3
5.5
–
6.3
6.7
4.6
7.6
6.4
–
1650
9.7
8.6
the total yield of monoꢀ and diglycolides of isovaleric (total yield of monoꢀ and diglycerides of isovaleric
acid to 26.8%. The highest yield (20.1%) of isovaleric acid, 29.3%) (2). The highest yield of diglyceride
acid diglycolide was obtained at an [isobutylene] : (13.3%) is observed at an [isobutylene] : [glycerol]
[ethylene glycol] ratio of 2 : 1. Note that the highest ratio of 2 : 1 (100
yield of isovaleric acid monoglycolide (25.0%) is (entry 1). The highest yield of isovaleric acid triglycerꢀ
observed at an [isobutylene] : [ethylene glycol] ratio of ide (8.6%) was found at a reactant ratio of 3 : 1 (100°С;
°С; 2.0 MPa; reaction time, 2 h)
1 : 1 and a CO pressure of 2.5 MPa.
2.0 MPa; reaction time, 3 h) (entry 9).
Note that at reactants (isobutylene, glycerol) ratios
= 100 С, рСО = 2.0 MPa, = 3 h) (entry 8)
between the components of the catalytic system. The and 2 : 1 ( = 100–110 С, рСО = 2.0– 2.5 MPa,
The reactant to catalyst ratio has a noticeable effect
on the yield of the products, as well as the ratio of 1 : 1 (
Т
°
τ
Т
°
τ
=
dependences of the product yields on the component 2–4 h) (entries 1–3, 5, 7), the formation of only
ratio of the catalytic system are nonmonotonic in monoꢀ and diglycerides of isovaleric acid was
character (Table 1, entries 3, 17–20), the optimal observed. It is interesting that a mixture of diꢀ and trigꢀ
[
Pd(Acac)2] : [PPh3] : [TsOH] ratio is 1 : 7 : 12. The lycerides of isovaleric acid formed at the 2 : 1 ratio of
optimal ratio of the reactants and catalyst is [isobutyꢀ the reactants under different conditions of the proꢀ
lene] : [ethylene glycol] : [Pd] = 550 : 550 : 1.
cess—
= 100
1 ratio
Т
°
= 90
С, рСО = 1.5 MPa,
= 100 С, рСО = 2.0 MPa,
°
С, рСО = 2.0 MPa,
= 3 h (entry 6). At the 3 :
= 3 h) (entry 9),
τ
= 3 h (entry 4) and
Т
τ
It was found that the carbonylation of isobutylene
with CO and glycerol in the presence of the
Pd(Acac)2–PPh3–TsOH system yields a mixture of
monoꢀ and diglycerides or monoꢀ, diꢀ, and triglycerꢀ
ides of isovaleric acid depending on the ratio between
the reactants (isobutylene, glycerol).
Table 2 shows the results of study of the influence of
different reaction conditions for isobutylene hydroesꢀ
terification with CO and glycerol in the presence of the
Pd(Acac)2–PPh3–TsOH system on the yield of
monoꢀ, diꢀ, and triglycerides of isovaleric acid. It can
be seen that the dependences of the product yields on
(Т
°
τ
the triglyceride with a yield of 8.6% is produced along
with the monoꢀ and diglycerides.
The elemental analysis and IR data for the syntheꢀ
sized monoꢀ and diglycolides and monoꢀ, diꢀ, and
triglycerides of isovaleric acid were reported in [6].
Tables 3 and 4 present the 1 H and 13C NMR data for
the obtained isovaleric acid glycolides (1) and (2) and
glycerides (3)–(5), which are completely consistent
with their structure [11, 12].
The catalytic activity of the Pd(Acac)2, Pd(PPh3)4
the reaction conditions (temperature, carbon monoxꢀ and PdCl2(PPh3)2 complexes and a number of binary
ide pressure, and reaction time) are nonmonotonic. and ternary systems based on the complexes in the
The ratio of the reactants (isobutylene, glycerol) is of isobutylene hydroalkoxycarbonylation reaction with
considerable importance (entries 2, 8, 9). The optimal CO and ethylene glycol under the found optimal conꢀ
ratio was found to be [isobutylene] : [glycerol] = 2 : 1 ditions ([isobutylene] : [ethylene glycol] : [Pd] = 550 :
PETROLEUM CHEMISTRY Vol. 52
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2012

192
SUERBAEV et al.
Table 3. 1H NMR data for glycolides and glycerides of isovaleric acid
1H NMR,
CH2–O
δ
, ppm (J, Hz)
CH2–OH
Compound
O
C
CH3
CH
CH–O
CH–OH
OH
CH2
1
2
0.81 d (6.5)
0.82 d (6.4)
1.97 m
1.98 m
2.07 d (7.0) 4.03 t (4.9) 3.63 t (4.9)
2.07 d (7.0) 4.06 t (4.8)
–
–
–
–
3.90 br.s
–
–
4.05 t (4.8)
3
4
5
0.86 d (6.5)
2.00 m
1.99 m
2.00 m
2.13 d (6.9) 4.02 d (5.4) 3.48 dd
–
3.82 m
3.6 d 3.66 t
(11.8; 6.5)
3.57 dd
(11.2; 3.2)
0.85 d (6.4)
2.11 d.(7.0) 3.97 dd.
(11.3; 4.9)
–
–
4.04 t (4.8) 3.61 d
4.10 dd
(10.8; 6.5)
0.84 d (7.4)
0.85 d (6.5)
2.09 d (7.0) 4.05 dd
2.12 (6.9) (4.8; 5.9)
4.22 dd
–
5.17 um.
–
–
(11.8; 4.3)
Table 4. 13C NMR data for glycolides and glycerides of isovaleric acid
13C NMR,
δ
, ppm
Compound
OO
O
C
CH2–O
CH2–OH
CH3
CH
CH–O
CCHH CCH
22
1
2
173.85
172.89
65.85
62.12
60.73
–
22.55
27.66
27.63
43.45
43.38
–
–
22.59
22.54
3
4
5
173.92
173.46
65.21
65.13
62.35
63.72
–
22.65
22.60
25.92
25.91
43.48
43.42
70.48
72.30
65.14
172.73
172.30
–
22.57
22.53
25.86
25.90
43.33
43.40
550 : 1,
Т
= 100°С,
рСО = 2.0 MPa,
τ
= 3 h) for this Pd(PPh3)4 and PdCl2(PPh3)2 complexes. Only the
reaction in the presence of the Pd(Acac)2–PPh3–
TsOH system was determined. Note that higher yields
of diglycolides are observed in the presence of the sysꢀ
tems based on Pd(PPh3)4. Their yield in the presence
of the Pd(PPh3)4–PPh3–TsOH system reaches 19.9%
(at a total yield of glycolides of 31.4%).
Pd(Acac)2–PPh3–TsOH (1 : 7 : 12), Pd(PPh3)4–
PPh3–TsOH (1 : 3 : 12) and Pd(PPh3)4–TsOH (1 : 12)
systems exhibit a high activity; the total yields of glyꢀ
colides are 41.8, 31.3 and 21.4%, respectively. A low
catalytic activity was shown by the PdCl2(PPh3)2–
PPh3–TsOH system (yield of glycolides, 4.3%) and
PdCl2–PPh3–TsOH (yield of glycolides, 0.4%). The
PdCl2–dppm–TsOH and PdCl2–dppe–TsOH (dppm =
bisꢀ(diphenylphosphino)methane, dppe = bis(dipheꢀ
nylphosphino)ethane) catalytic systems did not disꢀ
In summary, studying the effect of the conditions of
the reaction of isobutylene hydroalkoxycarbonylation
with CO and ethylene glycol (glycerol), we have deterꢀ
mined the relative catalytic activity of a number of
binary and ternary systems based on Pd(Acac)2, play the catalytic activity in the reactions in question.
PETROLEUM CHEMISTRY Vol. 52
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HYDROALKOXYCARBONYLATION OF ISOBUTYLENE WITH POLYHYDRIC ALCOHOLS
193
6. H. A. Suerbaev, E. G. Chepaikin, B. Zh. Dzhiembaev,
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