Cross-metathesis of methyl 10-undecenoate with dimethyl maleate: An efficient protocol with nearly quantitative yields

Article abstract of DOI:10.1039/c3ra47671e

In this cross metathesis of the renewable raw material methyl 10-undecenoate with dimethyl maleate, an α,ω-difunctional product was produced. Detailed optimizations led to nearly quantitative yields of the desired product. The cross metathesis of methyl 10-undecenoate with methyl acrylate yielded high conversions of the substrate. The product was accessed under mild reaction conditions with the use of a small amount of a commercially available homogeneous ruthenium catalyst. The in situ synthesis of dimethyl maleate from maleic anhydride was also possible in this reaction system. This journal is the Partner Organisations 2014.

Full text of DOI:10.1039/c3ra47671e

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Cross-metathesis of methyl 10-undecenoate with
dimethyl maleate: an efficient protocol with nearly
quantitative yields
Cite this: RSC Adv., 2014, 4, 16320
*
A. Behr, S. Toepell and S. Harmuth
In this cross metathesis of the renewable raw material methyl 10-undecenoate with dimethyl maleate, an
a,u-difunctional product was produced. Detailed optimizations led to nearly quantitative yields of the
desired product. The cross metathesis of methyl 10-undecenoate with methyl acrylate yielded high
conversions of the substrate. The product was accessed under mild reaction conditions with the use of a
small amount of a commercially available homogeneous ruthenium catalyst. The in situ synthesis of
dimethyl maleate from maleic anhydride was also possible in this reaction system.
Received 16th December 2013
Accepted 20th March 2014
DOI: 10.1039/c3ra47671e
www.rsc.org/advances
The resulting product was the a,u-dicarboxylic acid methyl
ester 3 with methyl acrylate 4 as a by-product (Fig. 1).
Introduction
The product 3 can be used in the manufacture for high-
molecular weight polyesters, polyamides and as a macrocyclic
compound, because of its a,u-difunctional system.13 Moreover,
dicarboxylic-derivatives are important intermediates for
synthesizing biodegradable polymers used in the production of
lubricants and plasticizers, and are therefore important inter-
mediates in chemical engineering.13–15 3 was achieved in 2007
through a cross metathesis with methyl acrylate by Meier et al.,
resulting in satisfactory yields.16
Detailed investigations of the cross metathesis of methyl 10-
undecenoate 1 with diethyl maleate have been performed. As a
result, a reaction network was identied that resulted in high
product yields.17
In terms of the resource-intensive processing required for
oleochemical research, positive contributions to protect the
reserves of existing fossil fuels can be made, or these petro-
chemicals can be partially substituted by using renewable
resources. The link between oleo- and petrochemistry is the rst
step toward generating new and conventional products in a
more environmentally-friendly way by using renewable
resources. Oleochemical metathesis plays an important role in
generating a broad range of mainly difunctional substrates,
which are interesting starting materials for the polymer
industry.1–6
Castor oil is the renewable source material used to produce
methyl 10-undecenoate for these experiments. To obtain pure
oil, several steps to rene it had to be taken. Detailed infor-
mation pertaining to the regeneration was reviewed by Meier
et al.7 Undecenoic acid was derived from the thermal cleavage of
ricinoleic acid, followed by transesterication, methyl 10-
undecenoate could be produced. Undecenoic acid and its cor-
responding methyl ester have great potential for industrial
applications, for example, for use as a basic building block in
the production of polyesters, polyolens or polyethers.8 Their
fungicidal and bactericidal properties further enhance this
broad range of applications.9
Several descriptions of metathesis reactions of maleic acid-
derivatives have been published. For example, the isomeriza-
tion of dimethyl maleate and fumarate during their self-
metathesis,18 as well as the investigations of the low reactivity of
methyl maleate in cross metathesis with ethylene.19 Methyl
The second substrate of our work was dimethyl maleate. It
can be generated by acid10 or TMSCHN2 (trimethylsilyldiazo-
methane)11 catalyzed reactions of maleic anhydride, or by
esterication of maleic acid in methanol.12
This article describes the ruthenium catalyzed cross
metathesis of methyl 10-undecenoate 1 and dimethyl maleate 2.
Department of Biochemical and Chemical Engineering, Chair of Technical Chemistry,
Technical University Dortmund, Emil-Figge-Str. 66, 44227 Dortmund, Germany.
E-mail: arno.behr@bci.tu-dortmund.de
Fig. 1 Cross metathesis of methyl 10-undencenoate 1 and dimethyl
maleate 2.
16320 | RSC Adv., 2014, 4, 16320–16326
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Results
Only the primary metathesis products are specied for the
results of this portion of the experiment. Therefore, only those
substrates with a double bond in the position shown in the
gures before are listed. However, slice deviations may appear
in the yields and conversions. The yields of 3 and 5 contain the
respective cis- and trans-isomeres of the substrates. The
described reactions of this work were carried out in closed
reactors to prevent the escape of the formed ethylene. The
catalyst system was of great importance for controlling the
reaction. No reliable conclusions as to the reactivity of a
substrate were made prior to optimizing a system, though
several approaches were used as guidelines.37,38 First, a detailed
catalyst screening with the homogeneous ruthenium complexes
[Ru]-1 to [Ru]-13 was carried out (Fig. 3).
Methyl 10-undecenoate 1 and dimethyl maleate 2 in a ratio of
1/10 were stirred for 3 hours at 50 ꢀC in toluene. A catalyst
concentration of 1 mol% (based on 1) was used. The catalysts
which were most likely in this reaction are available in Table 1.
Only the catalysts with a NHC-ligand showed noteworthy
results in this cross metathesis. As a result of the ligand, they
possess increased activity.39 In comparing the catalyst systems,
the catalysts with the 3-phenylindenylidene ligand were more
appropriate for the desired product 3 than the systems with the
benzylidene ligand. These ligands were found to have a greater
group tolerance than their benzylidene counterparts.38
Fig. 2 Self metathesis products of methyl 10-undecenoate 1.
acrylate 4 as by-product of the cross metathesis investigated was
easily separated from the reaction mixture by way of thermal
separation. It also has a broad spectrum of applications, for
example in comonomers for polymerization.20
Methyl acrylate 4 is manufactured at a large industrial scale
using acetylene, propylene or methyl formate, which are basic
petrochemical compounds.21–23 This substrate is both the
asymmetrical analogue to dimethyl maleate 2 and a widely-used
cosubstrate in oleochemistry.16,24–30
The self metathesis of methyl 10-undecenoate 1 to dimethyl
icos-10-enedioate 5 through the release of ethylene was the only
side reaction observed for the cross metathesis in question
(Fig. 2).
This C-20 dicarboxylic acid methyl ester 5 is also an inter-
mediate used in the synthesis of biodegradable polymers and is
therefore considered to be a value-added product.31 Different
methods for the cross metathesis of fatty-derivatives have been
published. Several of the cosubstrates include allylchloride,25
acrylo- and fumaronitril,25,26,32,33 acrolein,34 ethyl acrylate35 and
cis-2-buten-1,4-diyl diacetate.36
However, only a few means of cross metathesis with
symmetrical maleate esters have been published to this day.18
The oleochemical cross metathesis of methyl 10-undecenoate 1
with dimethyl maleate 2 under homogeneous catalysis is out-
lined below.
When using [Ru]-10, both quantitative conversion and yield
of 3 are possible. However, the disadvantage of this system was
the use of PhSiCl3 as an activating additive.40 The authors'
investigations were done without this catalyst due to its high
risk potential41 in accordance with the guidelines of “green
chemistry”.42 The catalyst for further investigations is [Ru]-4,
because for example this catalyst is stable at high
To the best of our knowledge, no systematic investigation of
this particular cross metathesis has been published to date.
Fig. 3 Investigated metathesis catalysts.
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Table 1 Best catalysts in the cross metathesis of 1 and 2. Reaction
conditions: T ¼ 50 ꢀC, t ¼ 3 h, solvent ¼ toluene, 1.0 mol% catalyst, 1/2:
1/10, * ¼ 100 eq. PhSiCl3 (based on catalyst)
was recorded aer a reaction time of 1 hour. As the reaction time
increased, yields of self metathesis product 5 increased pro-
portionally; therefore a constant reaction time of 1 hour had to
be capped in the subsequent optimization.
Catalyst
X (1) [%]
Y (3) [%]
Y (5) [%]
The ndings of the reaction temperatures investigated
clearly demonstrated that an increase in temperature resulted
in an increase of conversion and in product yields (Fig. 4).
At the same time, the conversion of 5 decreased. This yield
[Ru]-2
[Ru]-4
[Ru]-9*
[Ru]-10*
[Ru]-11*
71
92
49
>99
49
32
50
26
99
18
13
17
0
0
1
ꢀ
was reduced to 1% at a reaction temperature of 80 C. Under
these reaction conditions, the conversion of methyl 10-unde-
cenoate 1, as well as the yield of 3 are nearly quantitative at
>99%. The positive effect of the reaction temperature was
attributed to decreases in substrate viscosity. The resulting
acceleration of transport processed of catalyst to substrate was
simplied. Also the thermal activation of the cosubstrate 2
seemed to be necessary due to its stericꢀhindrance.
Table 2 Variation of the catalyst concentration in the CM of 1 and 2.
Reaction conditions: T ¼ 50 ꢀC, t ¼ 3 h, solvent ¼ toluene, catalyst ¼
[Ru]-4, 1/2: 1/10
Concentration [mol%]
X (1) [%]
Y (3) [%]
Y (5) [%]
By maintaining a temperature of 80 C, an isomerization of
the substrates was prevented, which arise with increasing
temperature. Different solvents were investigated to account
possible coordinative effects. Had this not been applied, a clear
classication within the different solvents could not have
showed any clear trend. Comparably high yields could be
reached with the standard metathesis solvents ethyl acetate and
dichloromethane. Lower yields and conversion (20%) were
generated using simple alcohols such as methanol and iso-
0.1
0.25
0.5
0.75
1.0
1.5
11
34
59
80
92
3
10
26
50
50
70
99
7
14
19
19
17
14
2
96
>99
2.0
temperatures.43 The objective of the further investigations is to propanol. Toluene was used in subsequent investigations as it
achieve results comparable to [Ru]-10 by using the catalyst resulted in the highest yields, and due to its low production
system [Ru]-4.
costs compared to the other solvents tested, which was partic-
The variation of the catalyst concentration within the range ularly benecial.44
of 0.1 mol% to 2.0 mol% produced a signicant trend in the
yields to product 3 (Table 2).
It should be noted that increasing the catalyst concentration
increased the conversion of methyl 10-undecenoate 1 and the
yields of 3. The course of the parallel undergoing self metathesis
is remarkable. The yields of 5 rst increased, but then fell to a
minimum at a concentration of 2.0 mol%. The same series of
experiments was carried out with a reaction time of 24 hours to
avoid side reactions. Identical results were achieved, so no side
reactions could proceed.
Quantitative conversions and yields were possible at a high
catalyst concentration of 2.0 mol%, but the nancial burden of
the catalyst was prohibitive. Also at this concentration an
isomerization of the oleochemical compound 1 could be
detected. Therefore, a concentration of 0.75 mol% was used for
subsequent investigations to determine whether similar results
Fig. 4 Variation of reaction temperature. Reaction conditions: t ¼ 1 h,
could be achieved with a reduced amount of catalyst.
solvent: toluene, catalyst: 0.75 mol% [Ru]-4, 1/2: 1/5.
Various tests with different ratio of substrate 1/2 in a range of
1/1 to 1/20 were carried out to reduce the amount of undesired
products and the unnecessary use of substrate. In general, the
self metathesis to 5 could be suppressed with an increased
excess of 2, which increased the yields of product 3 at the same
time. A compromise of high excess and high yields was reached
at a substrate–cosubstrate ratio (1/2) of 1/5. This ratio was
retained for subsequent steps in the experiment. To avoid
unnecessarily lengthy reaction times, different time experiments
were performed. They were carried out in the range of 5 minutes
to 24 hours. A constant conversion of methyl 10-undecenoate 1
Table 3 Variation of the catalyst concentration. Reaction conditions:
T ¼ 80 ꢀC, t ¼ 1 h, solvent: toluene, catalyst: [Ru]-4, 1/2: 1/5
Concentration [mol%]
X (1) [%]
Y (3) [%]
Y (5) [%]
0.1
0.25
0.5
0.75
1.0
44
56
81
>99
>99
8
16
51
99
99
18
19
14
1
1
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Having optimized the reaction conditions by this point, a
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As described previously, several investigations of the cross
second stage reduction of the catalyst concentration was carried metathesis have been published. These reactions were investi-
out to further reduce the amount of catalyst (Table 3). gated under the optimized reactions conditions of the metath-
0.75 mol% of the catalyst was sufficient to achieve nearly esis with dimethyl maleate 2 in order to verify whether the
quantitative conversions and yields. A further reduction of the relativities of the symmetric and asymmetric analogue mole-
concentration led to a collapse of the results of up to 50% of the cules result in the same yields, and whether direct conclusions
maximal value, which was therefore not useful.
for their use in other cross metathesis reactions could be drawn.
Environmentally friendly variations to the ratio of substrate
Under the same reaction conditions (80 ꢀC, ratio 1/4: 1/5,
to solvent were investigated, as the best solvent is no solvent in toluene), only 0.5 mol% of [Ru]-4 and a reaction time of 30
green chemistry. The ratio was tested within the range of 10 wt minutes were necessary to achieve 97% of the desired product 3.
% substrate up to no solvent at all (Fig. 5). The previous Hence, this reaction was faster, and a lower catalyst load was
attempts were made at 65 wt% substrate.
necessary than in cross metathesis with dimethyl maleate 2.
Fig. 5 shows that this cross metathesis is favored by a high The self metathesis to product 5 was not observed under these
substrate-concentration. At 60 wt% substrates, the resulting reaction conditions.
ongoing self metathesis was almost completely suppressed. A
further advantage was the reduced amount of solvent, making trends to the above-mentioned cross metathesis (Table 4).
the reaction more cost effective.45
Here only 30 wt% of the substrate, thus 70 wt% solvent,
The variation of substrate concentration showed similar
The same difunctional product 3 was generated via the cross yielded a nearly quantitative conversion and yield. The same
metathesis of methyl 10-undecenoate 1 and methyl acrylate 4 yields were also achieved without using a solvent. A reaction
(Fig. 6).
dilution was not necessary in this case, which was also observed
The advantage of this reaction is that no by-product was with dimethyl maleate 2. The investigation of the catalyst
observed except the self metathesis product of methyl 10- activity with methyl acrylate 4 as the cosubstrate demonstrated
undecenoate 1 the C-20 dicarboxylic acid methyl ester 5 (Fig. 2). that the same catalysts as those in the reaction with 2 were
The other product observed was dimethyl maleate 2, which active. Also, the same solvent effects were observed.
generated the same product 3, and was therefore not a typical
by-product.
Therefore, the optimized reaction conditions were almost
transferable to the unsymmetrical substrate. This point might
be applied to other cross metathesis systems, though this must
be tested in each case.
In situ preparation of dimethyl maleate 2 from maleic
anhydride 6
Having optimized the reactions conditions for the cross
metathesis of methyl 10-undecenoate 1 with dimethyl maleate
2, the in situ preparation of 2 from maleic anhydride 6 was
investigated, with subsequent use in cross metathesis (Fig. 7).
The use of maleic anhydride 6 enabled a 75% reduction in
costs, thanks to the cheaper production of the substrate. The
Table 4 Variation of substrate concentration. Reaction conditions:
T ¼ 80 ꢀC, t ¼ 30 min, solvent: toluene, catalyst: 0.5 mol% [Ru]-4, 1/4:
Fig. 5 Variation of substrate to solvent ratio. Reaction conditions: T ¼
80 ꢀC, t ¼ 1 h, solvent: toluene, catalyst: 0.75 mol% [Ru]-4, 1/2: 1/5.
1/5
Weight%
X (1) [%]
Y (3) [%]
10
20
30
40
50
94
97
>99
>99
>99
87
97
>99
>99
>99
Fig. 6 Cross metathesis of 1 and methyl acrylate 4.
Fig. 7 In situ preparation of dimethyl maleate 2.
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technical production process of maleic anhydride 6 is based on available catalyst [Ru]-4 (0.75 mol%) at 80 ꢀC, these high yields
the oxidation of hydrocarbons at high temperatures of between were achieved within a reaction time of 1 hour when using 2 as a
ꢀ
350 to 450 C. Maleic anhydride 6 has a broad range of appli- cosubstrate. With methyl acrylate 4, a lower amount of catalyst
cations, for example in the production of maleic acid, tartaric was necessary, and the reaction was completed within 30
acid, furanes and 1,4-butanediol.46 Therefore, this reaction was minutes. The conditions were very similar for both reactions,
of interest not only from an academic perspective, but also from which is a very important advantage for other cross metathesis
an economic point of view. Another advantage of the in situ compounds to be optimized within the same functional group.
cross metathesis, as demonstrated by many preliminary inves- It was possible to synthesize dimethyl maleate 2 in situ in the
tigations, is that maleic anhydride 6 is totally inactive in reaction, though further studies are necessary to determine
metathesis conversions with the type of catalysts used in this whether the basis of maleic anhydride 6 can achieve the high
investigation.
conversions described above.
At rst, the transformation of maleic anhydride 6 to dimethyl
maleate 2 was investigated without applying cross metathesis.
Therefore, different acids were used in methanol to react with
maleic anhydride 6 in different concentrations (sulfuric acid,
potassium hydrogen sulfate, dodecyl sulfonic acid, Dowex 1X8).
In this case, methanol performed two functions: it served both
as the solvent—no other solvent was used—and as the reagent
for converting the maleic anhydride 6.
Experimental
Analytic equipment and methods
Flash chromatography was conducted on silica gel 60 (Acros),
substrates were visualized with p-anisaldehyde reagent through
analytical thin-layer chromatography cards (VWR).
Both 1H- and 13C-nuclear magnetic resonance (NMR) spectra
were recorded in deuterated chloroform on a Bruker Avance
DRX 400 MHz and 500 MHz.
It turned out that Dowex 1X8 in an amount of 1 wt% (based
of 6) had the greatest impact on the formation of dimethyl
maleate 2. That detection had the benet of allowing the acid to
separate easily via ltration aer the reaction. The cross
metathesis was carried out under the above-mentioned reaction
conditions with the addition of 1 wt% Dowex and maleic
anhydride 6 instead of dimethyl maleate 2 and under an
increased reaction time of 12 hours (1/6 in a ratio of 1/5, solvent
Gas chromatography (GC) analysis of the reaction solutions
was carried out on a Hewlett-Packard gas chromatograph Series
6890 equipped with a HP5 capillary column (coating: 5%
diphenyl-95%-dimethoxy-polysiloxane; length 30 m; diameter
0.25 mm, thickness 0.25 mm). A ame ionization detector (FID)
connected to an autosampler was used to detect individual
components. The oven temperature program was as follows:
initial temperature 130 ꢀC, hold for 6 min, increase by 25 ꢀC
ꢀ
& reagent: methanol, 12 hours, 80 C, 1 wt% Dowex, 1.0 mol%
[Ru]-4). Under these conditions, the self metathesis of methyl
10-undecenoate 1 to 5 occurred at 9%. However, only a
conversion of 1 of about 60% and a 40% yield of 3 were ach-
ieved. These low values were explained by the use of methanol,
which resulted also in lower yields when using it in the cross
metathesis with dimethyl maleate 2. Another reason for these
results may have been the heterogeneity of the systems, which
occurred by adding a solid component to the homogeneous
system, and which may have resulted in mass transport limi-
tations and therefore lowered conversions and yields.
It was determined that it is, in principle, possible to use
maleic anhydride 6 rather than dimethyl maleate 2, which could
be more attractive in terms of cost. However, under the opti-
mized reaction conditions of the cross metathesis with
dimethyl maleate 2, only low yields were achieved. This problem
might be solved by using another catalyst system that is stable
in acid media and is highly active in methanol. Therefore, more
detailed investigations should be conducted.
minꢁ1 up to 320 C, hold for 4 min. Measurements were per-
ꢀ
formed in split–split mode (ratio 70 : 1) using nitrogen as a
carrier gas. The qualitative assignment of the chromatograph-
ically determined retention times of the individual components
was carried out by comparing them to their respective pure
substances. The quantitative determinations were made by the
method with an internal standard.
The mass spectra were recorded by GC/MS. The mass spec-
trometer was a Hewlett Packard 5973 with electron energy of
70 eV and a scan range [m/z] of 50–700. The oven temperature
program, the split–split mode and the specication of the
carrier gas were similar to those in the GC-FID method.
Materials
Undecenoic acid (99%), maleic acid (99%), methanol (99.8%),
methyl acrylate (99%), solvents and reagents were purchased
from Acros. The benzylidene ruthenium catalysts ([Ru]-1 and
[Ru]-2]) were obtained from Sigma-Aldrich, the thioether-cata-
lysts ([Ru]-12 and [Ru]-13) were provided by Evonik Industries
and the remaining indenylidene catalysts ([Ru]-3 till [Ru]-11)
were provided by Umicore and were used as received.
Conclusion
A systematic optimization of the reaction parameters with the
oleochemical raw material methyl 10-undecenoate 1 in cross
metathesis was conducted successfully. The metathesis in
question offers provided access to value-added and other
interesting sustainable intermediates with the basic petro-
Experimental procedures
Cross-metathesis of methyl 10-undecoate 1 with dimethyl
chemical metathesis partners, dimethyl maleate 2 and methyl maleate 2. All reactions were rst conducted under argon to
acrylate 4. Both reactions end in nearly quantitative yields of the check whether this was necessary. They were performed at least
desired product 3. Using a small amount of commercial twice to ensure accurate reproduction of the presented results.
16324 | RSC Adv., 2014, 4, 16320–16326
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When using 0.4 g (2 mmol) of methyl 10-undecenoate 1, 1.46
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1,20-Dimethyl-icos-10-enedioate 5. dH (500 MHz; CDCl3;
Me4Si): 1.21 (20 H, m, –CH2–), 1.58 (4 H, dd, J ¼ 7.1, 14.2, –CH2–
CH2–C(O)–), 1.96 (4 H, m, –CH–CH2–) 2.27 (4 H, t, J ¼ 7.6, –CH2–
C(O)–), 3.64 (6 H, s, –O–CH3–), 5.33 (2 H, s, –CH–); dC (125 MHz;
CDCl3; Me4Si): 24.9, 29.0, 29.1, 29.2, 29.3, 29.5, 32.5, 34.0, 51.4
(–O–CH3–), 130.2 (–CH–), 174.2 (–C(O)–); m/z: 369 (M+, 1%), 336
(9), 318 (2), 304 (4), 194 (1), 180 (2), 165 (2), 151 (3), 135 (4), 123
(5), 109 (9), 95 (20), 81 (27), 74 (25), 67 (28), 55 (64), 41 (39), 28
(100).
g (10 mmol) dimethyl maleate 2, 16.74 g toluene (90 weight%)
and an appropriate amount of catalyst, (1.0 mol% [Ru]-4 ¼
0.019 g, 0.02 mmol) were added. The reaction was carried out in
a closed reactor and heated to the desired temperature. Aer a
dened reaction time, the reactor was placed directly into an ice
bath to stop the reaction. Quenching the reaction by addition of
ethyl vinyl ether led to the same results, so this procedure is for
the examined reaction not necessary. Aer subsequent cooling,
the GC samples were weighed (0.1 g reaction solution, 0.4 g
isopropanol and 0.5 g n-pentadecane as internal standard) and
analyzed accordingly.
Acknowledgements
Cross-metathesis of methyl 10-undecenoate 1 with in situ
generated dimethyl maleate 2. When using 0.4 g (2 mmol) of
methyl 10-undecenoate 1, 0.99 g (10 mmol) maleic anhydride 6,
20.00 g methanol (90 weight% + excess for the reaction with
maleic anhydride 6) and an appropriate amount of catalyst, (1.0
mol% [Ru]-4 ¼ 0.019 g, 0.02 mmol) and 0.01 g Dowex 1X8 (1 wt
% based on 6) were added. The reaction, the sample preparation
and the product isolation occurred analogous to the cross
metathesis described above.
This work received nancial support from the German Federal
Ministry of Food, Agriculture and Consumer Protection (repre-
sented by the Fachagentur Nachwachsende Rohstoffe) and the
Emery Oleochemicals GmbH. The authors would like to thank
Umicore AG & Co. KG and Evonik Industries for their donations
of ruthenium metathesis catalysts.
Notes and references
1 M. A. R. Meier, Lipid Technol., 2008, 4, 84.
´
2 A. Behr, A. Westfechtel and J. Perez Gomes, Chem. Eng.
Technol., 2008, 31, 700.
Syntheses
Synthesis of methyl 10-undecenoate 1. 184.28 g (1.00 mol)
methyl undec-10-acid, 82 mL (2.00 mol) methanol and 4.52 g (26
mmol) p-toluenesulfonic acid were dissolved in 200 mL
dichloroethane and heated under reux for 48 hours. Aer
cooling to room temperature, the organic phase was washed
with 100 mL distilled water, 100 mL of a 5% solution of sodium
bicarbonate and once again with 100 mL of distilled water
consecutively. The solvent was removed under reduced pressure
aer drying with sodium sulfate. Finally, a fractional distillation
(82 ꢀC, 10ꢁ3 mbar) to isolate methyl 10-undecenoate 1 was
3 J. O. Metzger, Eur. J. Lipid Sci. Technol., 2009, 111, 865.
´
4 A. Behr and J. Perez Gomes, Eur. J. Lipid Sci. Technol., 2010,
112, 31.
5 A. Behr and S. Krema, Lipid Technol., 2011, 23, 156.
6 U. Biermann, U. Bornscheuer, M. A. R. Meier, J. O. Metzger
¨
and H. J. Schafer, Angew. Chem., Int. Ed., 2011, 50, 3854.
7 H. Mutlu and M. A. R. Meier, Eur. J. Lipid Sci. Technol., 2010,
112, 10.
8 B. B. Marvey, Int. J. Mol. Sci., 2008, 9, 1393.
9 F. C. Naughton, J. Am. Oil Chem. Soc., 1974, 51, 65.
carried out with a purity of about 99% as a clear, colorless 10 J. Clayden, N. Greeves, S. Waren and P. Worthers, Organic
liquid. Chemistry, Oxford University Press, 2001.
Synthesis of dimethyl maleate 2. 58.05 g (0.50 mol) maleic 11 S. C. Fields, W. H. Dent III, F. R. Green III and
acid is dissolved in 128.16 g (4.00 mol) methanol. 5.00 g E. G. Tromiczak, Tetrahedron Lett., 1996, 37, 1967.
(51 mmol) of concentrated sulfuric acid were added. The reac- 12 I. W. Ashworth, E. Bush, L. C. Chan, J. Cherryman, B. G. Cox
tion mixture was stirred overnight. Aer the reaction, the and J. Muir, Org. Process Res. Dev., 2012, 16, 1646.
resulting white solid was dissolved in 200 mL chloroform and 13 S. Warwel, H.-G. Jagers and S. Thomas, Fat Sci. Technol.,
the reaction mixture was washed three times with 100 mL of 1992, 9, 323.
distilled water each. Aer that the organic phase was dried over 14 J. C. Mol, J. Mol. Catal., 1994, 90, 185.
¨
´
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