Manufacture of C13 higher fatty acids from their esters by carbonylation of dodecene-1 in ionic liquid medium

Article abstract of DOI:10.1134/S096554411006006X

The effect of catalyst nature, temperature, acidity, promoters, and feedstock composition on dodecene-1 carbonylation in the presence of Pd compounds in an ionic liquid medium yielding higher fatty acid and their esters was studied. Palladium salts without phosphine ligands show high activity in tetrabutylammonium bromide. In systems of this kind, the catalyst is suspended in the reaction mass in the form of Pd particles with a size of 4-10 nm. It was shown that the catalytic system can be repeatedly used without loss of activity. It is acceptable to use synthesis gas instead of bare carbon monoxide with the selectivity for tride-canoic acid increasing.

Full text of DOI:10.1134/S096554411006006X

ISSN 0965ꢀ5441, Petroleum Chemistry, 2010, Vol. 50, No. 6, pp. 442–449. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.L. Lapidus, O.L. Eliseev, T.N. Bondarenko, N.H. Chau, 2010, published in Neftekhimiya, 2010, Vol. 50, No. 6, pp. 452–458.
Manufacture of C13 Higher Fatty Acids from their Esters
by Carbonylation of Dodeceneꢀ1 in Ionic Liquid Medium
A. L. Lapidusa, O. L. Eliseeva, T. N. Bondarenkoa, and N. H. Chaub
a Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
b Gubkin State University of Oil and Gas, Moscow, Russia
eꢀmail: oleg@server.ioc.ac.ru
Received April 20, 2010
Abstract—The effect of catalyst nature, temperature, acidity, promoters, and feedstock composition on
dodeceneꢀ1 carbonylation in the presence of Pd compounds in an ionic liquid medium yielding higher fatty
acid and their esters was studied. Palladium salts without phosphine ligands show high activity in tetrabutyꢀ
lammonium bromide. In systems of this kind, the catalyst is suspended in the reaction mass in the form of Pd
particles with a size of 4–10 nm. It was shown that the catalytic system can be repeatedly used without loss of
activity. It is acceptable to use synthesis gas instead of bare carbon monoxide with the selectivity for trideꢀ
canoic acid increasing.
DOI: 10.1134/S096554411006006X
Higher fatty acids (HFAs) are valuable products of
organic synthesis that find application in production
of plasticizers, flotation agents, emulsifiers, synthetic
detergents, consistent greases, paintwork materials,
and corrosion inhibitors [1, 2]. They are conventionꢀ
ally produced in industry by saponification of fats and
oxidation of higher paraffins with air on Mn catalysts.
The drawbacks of this method are a low yield of the
desired fraction; low selectivity; low product purity
owing to the impurities of dicarboxylic acids, ketoacꢀ
ids, and hydroxyacids; and a large volume of wastewaꢀ
ter [2, 3]. Recent years have seen a growth of interest
in the production of HFAs by homogeneous metal
complex catalysis processes, such as the preparation of
aldehydes from olefins followed by oxidation into
HFAs [4, 5] and the Reppe carbonylation of olefins
[6, 7]. Both methods ensure 100% utilization of
atoms, which is one of the key principles of “green
chemistry” [8]. The advantage of the former method is
that the technology of oxosynthesis is well developed
and a high selectivity for linear acids is attained. Howꢀ
ever, an additional stage of oxidation of aldehydes into
acids is required. In contrast, Reppe carbonylation is a
singleꢀstage method that allows obtaining esters and
anhydrides as well.
Recently, we have proposed a new approach to catꢀ
alytic synthesis of acids that consists in twoꢀphase carꢀ
bonylation of olefins and aldehydes by Pd complexes
using melts of organic salts (ionic liquids (ILs)) as the
polar phase [9–11]. In particular, we used a few examꢀ
ples to show that HFAs can be obtained with a high
yield in the presence of the Pd(OAc)2/HX/TBAB cataꢀ
lytic system (HX is an inorganic acid, TBAB is tetꢀ
rabutylammonium bromide) [10]. An important
advantage of this system is the possibility of excluding
phosphine complexes of Pd indispensable to the
Reppe carbonylation reaction conducted in convenꢀ
tional solvents [6, 7]. This circumstance appreciably
simplifies the catalytic system, makes it less expensive,
and prevents the product acids from contamination
with toxic triarylphosphines and their degradation
products.
In this work, we studied the model reaction of carꢀ
bonylation of dodeceneꢀ1 into С13 acids and their
esters in the presence of salts and Pd complexes. The
effect of the parameters of the process, the composiꢀ
tion of the catalytic system, and the nature of the
nucleophile on the yield of carboxylic acids and selecꢀ
tivity of the reaction was examined. The possibility of
reuse of the catalyst without loss of its activity was
demonstrated.
Palladium catalysts are the most active in olefin
carbonylation catalysts [6]; however, they are rather
expensive. Therefore, in order to develop an industrial
process for the manufacturing of HFAs on the basis of
the Reppe reaction, it is necessary not only to create
an active catalyst, but also to ensure its thorough sepꢀ
aration from the reaction products and recycling withꢀ
out loss of activity.
EXPERIMENTAL
Dodeceneꢀ1 (Aldrich, 95% purity) was additionꢀ
ally distilled under vacuum. Tetrabutylammonium
bromide (TBAB), tetrabutylammonium chloride
(TBAC) and 1ꢀbutylꢀ3ꢀmethylimidazolium ([bmim]+
)
salts (Acros Organics, Fluka, and Merck; 98–99%
442

MANUFACTURE OF C13 HIGHER FATTY ACIDS
443
Table 1. Hydroxycarbonylation of dodeceneꢀ1. Conditions: 2.26 mmol of dodeceneꢀ1, 11.3 mmol of H2O, 4.5 μmol of [Pd],
0.45 mmol of TsOH ⋅ H2O, and 1 g of IL; 110°C; 3.0 MPa, 2 h
Selectivity for acids, %*
Dodecene Yield of acids,
No.
Catalyst
IL
conversion, %
%
1
2
3 + 4
1
2
3
4
5
6
7
8
9
PdCl2
TBAB
90.8
85.5
15.1
12.1
90
88.7
83.3
12.4
11.7
86.5
87.6
81.7
66.8
80.3
18.5
8.7
40.9
38.5
31.5
41.0
38.4
41.2
43.0
53.1
48.4
40.0
58.6
46.7
48.9
30.9
34.9
37.2
46.0
35.9
36.0
35.3
36.4
29.3
36.5
56.8
41.4
51.6
37.5
29.1
24.1
24.2
22.5
23.1
25.7
23.5
20.7
17.5
15.1
3.2
Pd(OAc)2
TBAB
Pd(OAc)2
TBAC
Pd(OAc)2
[bmim]Br
TBAB
PdCl2Py2
Pd(SALEN)
PdCl2(polyVP)
PdCl2(PPh3)2
PdCl2(PPh3)2
TBAB
90
TBAB
86.8
71.8
82.4
21.1
10.5
39.2
23.7
10.8
TBAB
TBAC
10 PdCl2(PPh3)2
11 PdCl2(PPh3)2
12 PdCl2(PPh3)2
13 PdCl2(dppe)
[bmim]Br
[bmim]Cl
[bmim]BF4
TBAB
0.0
35.3
17.6
5.5
1.7
13.6
40.0
14 RhCl3
·
4H2O
TBAB
* Ratio between the yield of this acid to the total yield of acids.
purity) were used without additional purification. Carꢀ carrier gas, and
nꢀoctanol as an internal standard). For
bon monoxide of 99.7% purity was purchased from the quantitative determination of acids, they were prelimꢀ
OOO Redkino pilot production plant. Palladium
complexes were synthesized according to published
procedures [12–15].
inarily converted into methyl esters by treating the
ether extract with diazomethane.
Catalytic experiments were carried out in a 50ꢀml
steel reactor (with a glass insert) heated by an electric
furnace. Agitation was carried out using a magnetic
stirrer with a Teflon insert. In the standard experiꢀ
RESULTS AND DISCUSSION
Tridecanoic (1) and αꢀmethyllauric (2) acids are
ment, the charge was 2.26 mmol of dodeceneꢀ1, the major products of the carbonylation reaction of
11.3 mmol of H2O, 4.5 mol of Pd, 0.45 mmol of dodeceneꢀ1.
ꢀEthylundecanoic ( ) and ꢀpropylcaꢀ
TsOH H2O, and 1 g of TBAB; the reaction was carried
μ
α
3
α
⋅
prylic (
4
) acids are produced as well, although in
out at 110 and a pressure of 3.0 MPa for 2 h.
The reaction mixture was extracted with diethyl
ether, and the extract was analyzed on an Avtokhrom
°С
smaller amounts. They are obviously formed via the
migration of the double bond in dodecene followed by
carbonylation of dodeceneꢀ2 and dodeceneꢀ3. The
UE5 PID instrument (fusedꢀsilica capillary column ratio between the resultant isomeric С13 acids depends
30 m
×
0.25 mm, stationary phase SEꢀ30, helium as a on the catalyst nature and the reaction conditions,
C10H21CH=CH2 + CO + H2O
C12H25COOH + C10H21CH(CH3)COOH + C9H19CH(C2H5)COO(H) + C8H17CH(C3H7)COOH.
1
2
3
4
We have tested a number of Pd(II) compounds as chloride and palladium acetate and by complexes with
catalyst precursors (Table 1). The highest activity in weakly coordinating ligands—pyridine, SALEN bisꢀ
the TBAB medium was shown by the salts palladium Schiff base, and polyvinylpyridine. In the presence of
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444
LAPIDUS et al.
Table 2. Carbonylation of dodeceneꢀ1 in the presence of different nucleophiles. Conditions: 2.26 mmol of dodeceneꢀ1, 11.3 mmol of
H2O, 4.5 μmol of PdCl2(PPh3)2, 0.45 mmol of TsOH ⋅ H2O, and 1 g of TBAB; 110°C; 3.0 MPa, 2 h
Selectivity for acids and their esters, %
Dodecene
No.
Nucleophile
Yield, %
conversion, %
1
2
3 + 4
1
2
3
4
5
6
H2O
MeOH
ꢀPrOH
BuOH
ꢀBuOH
PhOH
71.8
45.8
43.4
45.5
47.3
30
66.8
42.3
39.4
41.8
46.3
0
53.1
51.5
66.0
61.7
58.5
–
29.3
33.6
30.7
32.1
30.7
–
17.5
14.9
3.3
i
6.2
s
10.8
–
these chemicals, the conversion of dodecene was 85– a lower degree of migration of the double bond in the
90% within 2 h and the yield of acids was 82–89% substrate in the medium of these ILs, so that the conꢀ
(Table 1, entries 1, 2, 5–7). Note that the catalysts centration of dodeceneꢀ2 and ꢀ3, which yields acids
3
remained in the homogeneous state in all cases; no and via carbonylation, is relatively low. Indeed,
4
precipitation of Pd black was detected.
according to the GLC data, the residual dodecene in
the reaction mass was weakly isomerized in these
experiments, thereby indicating the inhibition of acidꢀ
catalyzed transformations of the olefin.
The phosphine complexes of Pd in the TBAB
medium appeared to be less active: the yield of acids
was 67% on the PdCl2(PPh3)2 catalyst and only 18% on
PdCl2(dppe) (dppe = 1,2ꢀdiphenylphosphinoethane).
Rhodium chloride was also tested as a catalyst, and
Thus, strongly coordinating phosphines inhibit carboꢀ it showed a low activity; moreover, its regioselectivity
nylation, presumably because of competition with the appeared to be even lower than that of the palladium
substrate and CO for place in the Pd coordination catalysts (Table 1, entry 14).
sphere. At the same time, the selectivity for the linear
acid is higher in the presence of phosphine complexes.
It is of interest that, in the presence of PdCl2dppe, the
When using С1–С4 alcohols as nucleophiles, esters
corresponding to acids 1–4 can be obtained. However,
their yields are usually lower than those of acids. The
selectivity of the reaction is also determined by the
nucleophile nature. For water and methanol, approxꢀ
imately equal values of selectivity for esters 1–4 were
obtained, unlike in the case of alkoxycarbonylation of
higher alcohols in which the selectivity for ester of linꢀ
selectivity for acids
whereas the selectivity for acid
3
and
4
significantly decreased,
remained unchanged
2
as compared to the phosphineꢀfree catalysts (Table 1,
entry 13). It is likely that the lower selectivity is due to
the complexity of formation of the
πꢀcomplexes
Pd(dppe) with dodeceneꢀ2 and the steric strains creꢀ
ated by bulky ligands.
ear acid
1 increased, that for esters of acids 3 and 4
decreased, and the selectivity for ester of acid
2
The nature of IL has an effect on the activity and remained unchanged as compared to the hydroxycarꢀ
regioselectivity of the catalyst. For example, bonylation reaction. Attempts to use phenol as a
PdCl2(PPh3)2 is more active in the TBAC than in the nucleophile have been unsuccessful; the correspondꢀ
TBAB medium (Table 1, entries 8 and 9). In contrast, ing esters were not found in the reaction mixture
Pd(OAc)2 turned out to be almost inactive in the TBAC (Table 2).
medium (Table 1, entry 3). Thus, it is reasonable to use
An increase in the CO pressure facilitates a rise in
ligandꢀfree palladium (compounds that do contain
both the dodecene conversion and the yield of HFAs,
stabilizing phosphine ligands) and Pd phosphine comꢀ
with the most significant rise being observed at low
plexes in TBAB and TBAC, respectively.
pressures. For example, the yield of acids in the presꢀ
Ionic liquids based on 1ꢀbutylꢀ3ꢀmethylimidazoꢀ ence of catalyst Pd(OAc)2 in TBAB melt, increased
lium appeared to be unsuitable as a reaction medium; from 23 to 81% when the pressure increased from
the yield of acids in their presence was low. It is of atmospheric to 2 MPa and to 84% at 14 MPa. The
interest that isomeric acids
3 and 4 barely formed selectivity for acids 1 and 2 increased almost simultaꢀ
(Table 1, entries 10–12). This fact can be explained by neously with pressure, reaching 46–49% at 14 MPa.
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MANUFACTURE OF C13 HIGHER FATTY ACIDS
445
%
100
80
60
40
20
Yield of acids
Selectivity for
Selectivity for
Selectivity for
(1
(2
(3
)
)
) + (4)
0
2
4
6
8
10
12
14
, MPa
P
Fig. 1. Effect of pressure on the yield of higher fatty acids and the selectivity in the presence of Pd(OAc) . Conditions: 2.26 mmol
2
of dodeceneꢀ1, 11.3 mmol of H O, 4.5 µmol of Pd(OAc) , 0.45 mmol of TsOH·H O, and 1 g of TBAB; 110°C; 2 h.
2
2 2
Correspondingly, the selectivity for the remaining evident that the decrease in the selectivity for acids
3
acids ( and ) decreased (Fig. 1). Similar depenꢀ and with the increasing pressure is due to the supꢀ
3
4
4
dences were obtained for the phosphine complex of pression of doubleꢀbond migration in dodecene
Pd; however, its activity was in general lower and the responsible for the formation of these acids.
selectivity for the linear acid was higher. In addition,
The introduction of an additional amount of the
the rise in the selectivity for acids
1 and 2 with the
phosphine ligand into the catalytic system of olefin
carbonylation leads to an increase in the selectivity for
linear products, although the total yield generally
increasing pressure was somewhat slower than that for
Pd(OAc)2 (Fig. 2).
Many researchers note that the growth of partial decreases [7, 18]. We studied the hydroxycarbonylaꢀ
pressure of CO has a positive effect on the rate of carꢀ tion of dodeceneꢀ1 in the presence of the catalytic sysꢀ
bonylation of higher olefins (in conventional solvents) tem PdCl2(PPh3)2 + nPPh3, where n= 0…16. The subꢀ
and a negative effect on the selectivity for the linear strate conversion and the total yield of HFAs
acid [7]. in particular, it was pointed out [16, 17] that decreased with an increase in the amount of tripheꢀ
an increase in PCO results in a decrease in the selectivꢀ nylphosphine in the system. However, the yield of linꢀ
ity for a linear acid in the hydroxycarbonylation of ear acid 1 passes through a maximum at n = 4, whereas
octeneꢀ1 and hepteneꢀ1. The same conclusion was the yield of isomeric acids decreases monotonically.
drawn in [18, 19] for the hydroxyꢀ and methoxycarboꢀ The increase in the PPh3 content had an appreciably
nylation of noneneꢀ1 in the presence of the catalytic noticeable effect on the yields of
3 and 4, which
system PdCl2(PPh3)2 + PPh3. However, in the absence dropped to zero at = 16. The isomerization degree of
n
of excess phosphine, a variation in PCO over the range unreacted dodecene regularly decreased with an
of 7–24 atm had no effect on regioselectivity [18]. Our increase in the excess of PPh3 in the charge. The selecꢀ
results show that the
dependent on the pressure and the slight increase in content to attain 70% at
the selectivity for is explained by the decreased yield for the remaining acids monotonically decreased
of acids and . The results of monitoring the isomerꢀ (Fig. 3). Thus, the introduction of an additional
1
/
2
ratio, in contrast, is barely tivity for acid
1
increased monotonously with the PPh3
n
= 16, whereas the selectivity
1
3
4
ization of unreacted dodecene in the reaction mixture amount of the phosphine ligand can completely supꢀ
are consistent with this conclusion. The higher the CO press the migration of the double bond in olefin and
pressure, the lower the degree of isomerization. It is the yield of the corresponding isomeric acids and, at
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446
LAPIDUS et al.
%
100
Yield of acids
Selectivity for
Selectivity for
Selectivity for
(1
(2
(3
)
)
80
60
40
20
) + (4)
0
2
4
6
8
10
12
14
, MPa
P
Fig. 2. Effect of pressure on the yield of higher fatty acids and the selectivity in the presence of PdCl (PPh ) . Conditions:
2
3 2
2
2.26 mmol of dodeceneꢀ1, 11.3 mmol of H O, 4.5
110°C; 2 h.
µ
mol of PdCl (PPh ) , 0.45 mmol of TsOH·H O, and 1 g of TBAB;
2
2
3 2
the same time, increases the selectivity for the linear With increasing acidity of the medium, the selectivity
acid.
for linear acid 1 decreased from 54% (in the absence of
TsOH) to 38.5%. In this case, the decline in selectivity
was due to the advanced rise in the yield of isomeric
acids as compared to acid 1. We obtained similar
It was proposed to modify Pdꢀphosphine catalyst
by addition of tin chloride in order to increase the regiꢀ
oselectivity [20]. It is believed that the bulky hydride
complex HPd(SnCl3)(PPh3)2, which facilitates the
increase in the yields of esters of linear acids, is formed
in this process. Our results demonstrated that the
addition of SnCl2 results indeed in a certain increase in
regioselectivity. However, this effect is accompanied
by a decrease in the yield of acids proportionally to the
amount of SnCl2 introduced, whereas the selectivity
remains almost unchanged at Sn/Pd ratio > 1 (Fig. 4).
results using the catalyst PdCl2(PPh3)2. However, in
this case, the yield of HFAs in the absence of a proꢀ
moter was higher, 13.5%. It should be noted that durꢀ
ing the reaction over Pd(OAc)2 in the absence of an
acid promoter, the formation of Pd black was observed
at the end of the experiment. Apparently, the low yield
in this experiment was due not only to the absence of a
promoter, but also to the transition of a fraction of Pd
into heterogeneous state, in which it does not particiꢀ
pate in carbonylation.
The acidity of the medium is an important factor
having an effect on the activity and selectivity of the
catalyst. Promotion with strong inorganic acids
increases the concentration of Pd hydride complexes,
which are true olefin carbonylation catalysts [6, 7]. We
studied the effect of concentration of an acid promoter
on the yield and selectivity of the reaction in the presꢀ
ence of the catalyst Pd(OAc)2 in a TBAB medium. In
Reetz and de Vries [21] hypothesized that the staꢀ
bility of ligandꢀfree Pd in an IL melt is due to the forꢀ
mation of a stable metal suspension. A transmission
electron microscopy (TEM) image of the reaction
mass shows the presence of 4ꢀ to 10ꢀnm metal partiꢀ
1
the absence of pꢀtoluenesulfonic acid, which we used
cles (Fig. 5). Apparently, they do not exhibit catalytic
as a promoter, the reaction was very slow: the yield of
HFAs was 2.4% within 2 h. The introduction of 5 mol %
(with respect to dodecene) TsOH resulted in an
increase of the yield to 71%, and the yield of HFAs at
a promoter content of 20 mol % was 83.3% for 2 h.
activity of their own; rather, they are a source of Pd
1
We are grateful to Dr. of Physics and Mathematics D.V. Shtanꢀ
skii (Moscow Institute of Steel and Alloys) for making TEM
images.
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MANUFACTURE OF C13 HIGHER FATTY ACIDS
Yield of acids
447
%
100
Selectivity for
Selectivity for
Selectivity for
(
(
(
1
2
3
)
)
80
60
40
20
) + (4)
0
2
4
6
8
10
12
14
16
PPh3/PdCl2(PPh3)2, mol/mol
Fig. 3. Effect of PPh additive on the yield of higher fatty acids and selectivity. Conditions: 2.26 mmol of dodeceneꢀ1, 11.3 mmol
3
of H O, 4.5 µmol of PdCl (PPh ) , 0.45 mmol of TsOH·H O, and 1 g of TBAC; 110°C; 0.5 MPa, 2 h.
2
2 3 2 2
atoms to detach from their surface and to coordinate a hydroxycarbonylation of dodeceneꢀ1 into higher fatty
acids was demonstrated.
proton, olefin, and CO.
The necessity to use pure carbon monoxide instead
of less expensive synthesis gas is considered to be a
drawback of functionalization of olefins by carbonylaꢀ
tion as compared to the oxo synthesis [7]. Therefore,
we examined how the replacement of CO with syntheꢀ
sis gas would affect the reaction parameters. It was
found that, with the synthesis gas having a composiꢀ
tion of CO : Н2 = 1 : 2, the yield of acids decreased to
63 vs. 69% in the experiment with pure CO (РСО was
1 MPa in both experiments). At the same time, the
In a series of experiments, we demonstrated that
the use of TBAB as a medium for the hydroxycarboxꢀ
ylation of dodeceneꢀ1 provides an opportunity for the
recycling of the catalytic system without loss of the
activity. We employed the extraction of the reaction
mixtures with hexane to isolate the reaction products.
In this process, the fatty acids synthesized and unreꢀ
acted dodecene pass to the hexane solution, while the
catalyst remains in the system and can be used for carꢀ
bonylation of a new portion of feedstock. Water is a
reactant, and the corresponding amount of it should
also be added. It is noteworthy that all procedures can
be carried out in air, thereby considerably simplifying
the process.
selectivity for linear acid
and the selectivity for acids
1
increased from 33 to 40%
and dropped from 31.5
3
4
to 24%. In the experiments with the synthesis gas of
1 : 1 composition (РСО = 2 MPa), the yield of acids was
almost the same as that observed in the experiment
with pure CO under a pressure of 2 MPa, i.e., 81%.
The catalyst was recycled ten times, in which the
HFA yield varied from 81 to 89%. The sixth run, in
which the yield decreased to 77%, was an exception.
We attributed this fact to the gradual washout of the
promoter TsOH from the reaction mixture during the
repeated extractions with hexane. Indeed, in the next
experiment, when TsOH was added into the reactor,
the HFA yield returned to the previous high values.
Thus, the efficiency of the simple and inexpensive proꢀ
The selectivity for acid
1
also increased from 35 to 44%
decreased from 29 to 19%.
and that for acids and
3
4
Thus, the feasibility of the reaction in the synthesis gas
was shown. in this case, the catalyst activity is not
lower at an appreciably high partial pressure of CO
does not decrease and the regioselectivity is enhanced
as a result of suppression of doubleꢀbond migration in
dodecene and, hence, a decrease in the yield of isoꢀ
cedure for recycling a homogeneous catalyst for the meric acids
3 and 4.
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448
LAPIDUS et al.
%
100
Yield of acids
Selectivity for
Selectivity for
Selectivity for
(1
(2
(3
)
)
80
60
40
20
) + (4)
0
8
14
SnCl /PdCl (PPh ) , mol/mol
2
2
3 2
Fig. 4. Effect of SnCl additive on the yield of higher fatty acids and selectivity. Conditions: 2.26 mmol of dodeceneꢀ1, 11.3 mmol
2
of H O, 4.5 µmol of PdCl (PPh ) , 0.45 mmol of TsOH·H O, and 1 g of TBAC; 1106C; 3.0 MPa, 2 h.
2
2 3 2 2
50 nm
Fig. 5. TEM image of the reaction mixture of the hydroxycarbonylation of dodeceneꢀ1 in the presence of the
Pd(OAc) /TsOH/TBAB system.
2
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MANUFACTURE OF C13 HIGHER FATTY ACIDS
449
8. B. M. Trost, Angew. Chem., Int. Ed. Engl. 34, 259
In summary, we have studied the influence of variꢀ
ous factors on the carbonylation of dodeceneꢀ1 in the
presence of Pd compounds in ionic liquid media yieldꢀ
ing С13 fatty acids and their esters. It was shown that a
catalytic system without phosphine ligands can be
recycled without loss of activity. Moreover, it is acceptꢀ
able to use synthesis gas instead of pure carbon monꢀ
oxide as reactant.
(1997).
9. A. L. Lapidus, O. L. Eliseev, N. N. Stepin, and
T. N. Bondarenko, Izv. Akad. Nauk, Ser. Khim.,
No. 11, 2458 (2004).
10. O. L. Eliseev, N. N. Stepin, T. N. Bondarenko, and
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PETROLEUM CHEMISTRY Vol. 50
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2010