Sustainable route to methyl-9-hydroxononanoate (polymer precursor) by oxidative cleavage of fatty acid methyl ester from rapeseed oil

Article abstract of DOI:10.1039/c3gc41491d

Fatty acid methyl esters from rapeseed oil can be converted to monomers for polymer industries (85% methyl-9-hydroxynonanoate) by an oxydoreductive cleavage step in solvent free medium at room temperature, followed by a reduction step. All by-products are valuable and the reactions are performed under mild conditions.

Full text of DOI:10.1039/c3gc41491d

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DOI: 10.1039/C3GC41491D
Graphical abstract
Sustainable route to methyl-9-hydroxononanoate (polymer
precursor) by oxidative cleavage of fatty acid methyl ester from
rapeseed oil
a
a
a
b
c
Kévin Louis, Laurence Vivier, Jean-Marc Clacens, Markus Brandhorst, Jean-Luc Dubois,
a
a
Karine De Oliveira Vigier* and Y. Pouilloux*
FAME can be conveniently converted to 85% of methyl-9-hydroxynonanoate in three steps. All process by-products are
valuable.

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Cite this: DOI: 10.1039/c0xx00000x
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COMMUNICATION
Sustainable route to methyl-9-hydroxononanoate (polymer precursor)
by oxidative cleavage of fatty acid methyl ester from rapeseed oil
a
a
a
b
c
Kévin Louis, Laurence Vivier, Jean-Marc Clacens, Markus Brandhorst, Jean-Luc Dubois, Karine De
a
a
Oliveira Vigier* and Y. Pouilloux*
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
Fatty acid methyl esters from rapeseed oil can be converted to
chlorinated hydrocarbons (e.g. dichloromethane and chloroform)
monomer for polymer industries (85% of methyl 9- 50 leads to the formation of ozonides.
2
5-29
hydroxynonanoate) by an oxydoreductive cleavage in solvent
free medium at room temperature followed by a reduction
step. All by-products are valuable and the reactions are
performed under mild conditions.
Nevertheless, all the studies reported in the literature suffer
from a lack of selectivity to the desired product due to i) the
reactivity of intermediaries with protic solvents (see below), ii)
1
0
2
3
the utilization of reducers which can damage aldehyde function
(Zn/AcOH) or give rise to more complicated purification steps
5
6
6
5
0
5
3
0,31
The depletion of the fossil carbon reserve and the global warming
concern lead to the use of biomass as raw material. Biomass and
specifically vegetable oils with their long-chain and aliphatic
(Ph P/Ph PO).
3 3
1
2
2
3
3
4
4
5
0
5
0
5
0
5
1
-5
structure can be converted into polymers. Unsaturated fatty
acids contain two functions (a carbonyl and several unsaturated
bonds) where chemical reactions can be performed. Owing to
these properties, fatty acid derivatives contribute to flexibility,
toughness, light stability, biodegrability, and low toxicity of
6
,7
many plastics. For example, soybean oil is used in making bio-
8
,9
based polyols for polyurethane applications.
Many other
vegetable oils are used such as castor oil to produce bio-based
1
,10,11
epoxy resins,
oil derivatives
sunflower oil to provide high oleic sunflower
and bio-based nanocomposites from
1
2-15
1
6
epoxidized linseed oil. Vegetable oils can be converted to bio-
sourced polymer after oxidation of the FAME (Fatty Acid Methyl
Ester) to produce the corresponding aldehyde. After
hydrogenation of reductive amination, this aldehyde can be
transformed to monomer for polymer industries (Figure 1).
These products and other derivatives of polyunsaturated
vegetables oils have many potential uses (i.e. plasticizers,
polyamide plastics, wool treatment, and new coatings).
70
Figure 1.Synthesis of polyamide or polyester from FAME.
Herein the synthesis of methyl azelaaldehydate was performed
from methyl oleate and more largely from FAME of rapeseed oil.
The reaction was carried out in absence of solvent at room
temperature in the presence of Pd/C and hydrogen with yield and
purity over 90%. The catalyst was recycled and Pd leaching was
only 5 ppm. The hydrogenation of methyl azelaaldehydate was
investigated, and a 93% yield of corresponding alcohol (methyl
9-hydroxynonanoate) was obtained.
7
5
Ozonolysis is
a convenient and highly effective method
producing a large panel of compounds such as carboxylic acids,
ketones, aldehydes and alcohols. Several attempts were done to
favor the formation of aldehydes as main products by controlling
the double bonds ozonolysis of soybean oil, rapeseed oil and
8
0
1
7-21
canola oil, using different solvents or mixture of solvents.
Indeed, the nature of the solvent used plays an important role
during ozonolysis. Solvent may be classified, broadly, as
participating or non-participating agent. Participating solvents
will react chemically with intermediates formed during the
Oxydoreductive cleavage of methyl oleate and FAME
In a first set of experiments, methyl oleate was used as a model
molecule thanks to its mono-unsaturated structure to study the
ozonolysis reaction. Ozonolysis was performed through a
saturation of the solvent by ozone - at low temperature (i.e. -
22
ozonolysis reaction. For example, it is well-known that when
ozonolysis is carried out in a solvent such as alcohol or water,
which is a proton donor, it leads to the formation of hydrogen
8
5
7
8°C) - prior to the addition of unsaturated compounds which
2
3,24
peroxide.
On the other hand, the ozonolysis performed in
32
react instantaneously.
This procedure led to numerous
aprotic solvents such as hydrocarbons (e.g. pentane, hexane) and
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Green Chemistry
experimental damages as explosion due to free radical
decomposition of unstable intermediates (i.e. molozonides). In
similar to those obtained with methyl oleate.
3.134
60
65
70
the following experiments, the decomposition was prevented by
the addition of ozone in a mixture of methyl oleate and
dichloromethane at -78°C (Table S1). In these conditions, a lower
amount of ozone reacted instantaneously with the double bond of
methyl oleate limiting the amount of unstable molozonides.
Moreover, ozone quantity was reduced to 10%.
150
5.838
1
1
25
00
5
0
5
0
5
0
5
0
5
0
5
1
75
The selectivity to ozonides was followed by H NMR and HPLC
1
1
2
2
3
3
4
4
5
5
analysis at room temperature due to the decomposition of
ozonides in the GC injector. Indeed, ozonides are not stable at a
5
2
0
5
12.381
1
9
temperature higher than 50°C.
One should mention, that the
13.906
ozonides were stable at room temperature since no modification
or degradation were observed by H NMR analysis after several
1
11.049
5
10
Time (min)
15
weeks under nitrogen storage (Figure S1). The reaction was
performed with O /O bubbling (1.6 molar %) in CDCl at room
3
2
3
temperature. In these conditions, ozonides were formed with a 75 Figure 2. Reversed-phase HPLC chromatogram for the six ozonides of
high selectivity (> 99%).
methyl oleate. Conditions: ODS 3 µm, 150 x 2.1 mm, MeOH/H
2
O (92/8)
-
0.25 mL/min.
In dichloromethane, independently of the temperature (-78°C,
0°C or 25°C) the conversion of methyl oleate was total and
ozonides were selectively produced (Table S1). These results
show that the synthesis of methyl azelaaldehydate can be
performed in dichloromethane at room temperature without any
lack in selectivity. As shown by HPLC analysis (Figure 2),
molozonide decomposition led to three ozonides which have each
two isomers with a cis and trans configuration. The mechanism
of the ozonides formation is described in Figure S2. The
quantification of each ozonides was not possible. However,
independently of the reactions conditions, nonanal and methyl
azelaaldehydate were always obtained in similar amount. The
results are similar with other non protic solvent such as pentane,
hexane and heptanes at room temperature (100% of conversion
adn 99% of selectivity to ozonides, Table S1). One should point
out that when the reaction is performed at low temperature (-78°C
and 0°C), the precipitation of ozonides is observed for a
Next, the selective reduction of ozonides into aldehydes was
studied at room temperature to develop a one pot-two steps
process. Starting from the reaction media obtained from
ozonolysis reaction, a reducer was added after the elimination of
O excess by N bubbling. The idea was to use a reducer that can
form a by-product which can be valorized afterward. The ozonide
reduction was first studied in the presence of DMS, the by-
product being DMSO, a capital solvent in organic synthesis
8
8
9
9
0
5
0
5
2
2
(
Table 1, Entry 1). Unfortunately, the conversion of methyl oleate
was only 50% and the yield to aldehydes was 45%. When the
reaction was performed upon prolonged time (up to 17 h) the
conversion and the yield were not improved. DMS was thus
replaced by triphenylphosphine. The conversion of methyl oleate
was total and the selectivity to aldehydes was over 90% (Table 1,
Entry 2). One should note that even with this high activity, this
reducer cannot be recovered - as previously mentioned - from the
reaction media without using environmental unfriendly
-
1
concentration higher than 10 g.L of methyl oleate. The
ozonolysis of methyl oleate at room temperature allows its
conversion to ozonides at any concentration. Indeed, at room
temperature, methyl oleate ozonides are soluble in solvent and
liquid in solvent-free conditions. In order to develop ozonolysis
of methyl oleate in an environmental friendly process, an
experiment was performed with direct ozone bubbling (1.6 molar
31
compounds. Having all these results in hand, heterogeneous
catalysis reduction was investigated in environmental and
economic interest (Table 1). The reduction of methyl oleate
ozonides was studied in the presence of a commercial Pd/C
catalyst from Sigma Aldrich with 5wt% Pd at room temperature
00 under atmospheric pressure of H2 (200 ml/min). Water was
formed as by-product. The conversion (> 99%) and the yield
1
1
1
1
%) in methyl oleate, without solvent, at room temperature.
Solvent-free ozonolysis leads to same results than under solvent
conditions (Table S1).
(
92%) were similar to the ones obtained in the presence of
triphenylphosphine (Table 1, entry 3). Moreover, the reaction
time was divided by 17 since only 1 hour was necessary to reach
05 93% of methyl azelaaldehydate in the presence of Pd/C.
Conversion and yield were similar in solvent and solvent free
conditions. However, the reaction time was increased to 3 h in
the absence of solvent due to a lower solubility of hydrogen in
ozonides and saturated FAME (Table 1, Entry 4) than in the
10 presence of solvent (Table 1, Entry 3). Catalyst and products
This ozonolysis process was applied to FAME from rapeseed oil.
Rapeseed oil has a low level of saturated fats (~10 wt.%) along
with high levels of monounsaturated (MUFA, ~60 wt.%) and
polyunsaturated (PUFA, ~25 wt.%) fatty acids. All of MUFA
(mostly methyl oleate) and PUFA (methyl linoleate and α-
linolenate) contain carbon-carbon double bonds within their fatty
acyl groups which are readily available for chemical/structural
modifications. All these UFA led to C-9 aldehyde-ester/acid.
Ozonolysis of FAME from rapeseed oil was carried out without
solvent at room temperature as previously described (Table S1).
The conversion of unsaturations was total, saturated FAME did
not react during ozonolysis and was recovered at the end of the
reaction. Molar ratio between ozone and unsaturations was
TM
were easily separated by filtration on Whatman paper at room
temperature. Solvent was removed and the methyl
azelaaldehydate was purified either on silica column using
petroleum ether/diethyl ether (85/15) as eluent or by distillation
15 under vacuum (i.e. 8 mmHg) at respectively 49°C and 90°C for
nonanal and methyl azelaaldehydate. Silica column gave high
2
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Page 4 of 6
purity (~99%) but needed the use of solvent.
Table 1 : Reduction of ozonides from methyl oleate
0,6
0
0
,5
,4
40
5
0,3
0,2
0,1
0,0
a
Amount
of
Reducer
4 eq.
Yield (%)
Reaction
time (h)
Conv.
(%)
Entry
Reducer
DMS
4
5
2
3
1
2
5
17
50
>99
45
95
41
93
PPh
3
b
1.1 eq.
H
2
3
4
10 wt%
10 wt%
1
3
>99
>99
93
92
92
90
0
5
10
15
20
Pd(5)/C
c
2
H
50
Reaction time (h)
Pd(5)/C
Figure 3 : Conversion of ozonides of FAME from rapeseed oil with
1
different amounts of Pd(5)/C, followed by integrating H NMR ozonide
and ester signal. Conditions: Ozonides from FAME (28 mmol), H (200
mL.min ), room temperature, catalyst content: (○) 10 wt%, (▲) 7,5 wt%,
Conditions: Methyl oleate ozonides (3.4 mmol), CDCl
3
(50 mL), room
a
b
-1
c
temperature, Isolated yield,
H
2
(200 mL.min ), No solvent - H (200
2
2
-
1
-
1
mL.min )
55
(x) 5 wt%.
Distillation under vacuum afforded a free-solvent purification
step with a 93% purity of expected aldehyde-ester. Purity of
methyl azelaaldehydate as monomer is a critical point for the
functionalization and polymerization step afterwards (see below).
The recyclability of catalyst was then investigated by
removing the catalyst at the end of the reaction from the reaction
media by filtration. The recovered catalyst was washed with a
small amount of dichloromethane and dried under vacuum (150
1
0
One can note that the by-products of this reaction are water and 60 mbar) at 60 °C for 15 h before another cycle. After 9 runs, the
nonanal. The latter can be valorized in cosmetic industry for
example.
yield to methyl azelaaldehydate was unchanged showing the
stability of the catalyst in the reaction media (Figure S3). This
result, showing that the reduction step of ozonides can be
performed in a continuous flow reaction, is of prime importance.
65 The leaching of Pd in the reaction media was also studied by ICP
analysis. The amount of Pd in the crude mixture (5 ppm) is very
low. To be sure that this leaching is not responsible of the catalyst
activity, the solid was removed when the conversion reached
50%. After the removal of the catalyst, hydrogen was introduced
Table 2: Catalytic hydrogenation of ozonides from FAME of rapeseed oil
1
5
b
Catalyst amount
Reaction
time (h)
9.5
12.25
16.5
0.54
Yield
(%)
91
89
91
Entry
Catalyst
[a]
(wt%)
70
in the reaction media as previously described and the reaction
was performed for 1 h. No conversion of ozonides was observed
showing that the leaching of Pd did not allow the formation of
methyl azelaaldehydate. Pd(5)/C has high catalytic properties
without leaching in media and gives rise to high yields and
selectivity for catalytic reduction of FAME’s ozonides.
Moreover, this catalyst is recyclable.
1
2
3
4
Pd(5)/C
Pd(5)/C
Pd(5)/Cc
Pd(5)/C
10
7.5
5
10
92
-
1
2
Conditions: Ozonides from FAME (28 mmol) - H (200 mL.min ) -
b
a
room temperature. Until total conversion of starting material,
75
c
Isolated yield,
PH2 = 16 bars.
In order to improve this process, the amount of hydrogen used
in the reduction step was also investigated. Indeed, solvent-free
The catalytic reduction was applied to ozonides of FAME from
rapeseed oil directly in solvent-free media. This experiment was
2
2
3
3
0
5
0
5
bubbling of hydrogen requires a huge amount (138 eq.) of H due
2
undertaken at room temperature in the presence of Pd/C as 80 to the low solubility of H in ozonides compared to the reduction
2
catalyst under hydrogen bubbling directly in ozonides (Table 2,
Entry 1). In these conditions, the catalyst content was related to
the ozonides amount taking into account the total conversion of
unsaturations in FAME (Table S1). The yield to methyl
reaction in solvent media. When hydrogen was under pressure, its
solubility can be increased. Under a pressure of 16 bars of H2,
conversion and yield obtained were similar to those observed
under atmospheric pressure. However, the reaction time was
azelaaldehydate (91%) was similar to those obtained without 85 critically decreased (Table 2, Entry 4). The catalyst was always
solvent with ozonides from methyl oleate (Table 1, Entry 4). In
order to improve the catalytic process, the content of palladium
on activated carbon was kept to 5 wt% and the catalyst content
was varied from 5 to 10 wt% (Table 2, Entries 1 to 3). As
highly selective and did not reduce aldehyde function to alcohol.
With 16 bars of H , quantity of hydrogen was significantly
2
decreased to 20% (1.2 eq.). One can note that a pressure of 16
bars of hydrogen is required to convert totally ozonides to
expected, an increase from 5 to 10 wt% led to a decrease in the 90 aldehyde ester. Below this pressure of hydrogen the conversion
reaction time from 16.5 to 9.5 h to reach a total conversion of
ozonides (Figure 3). However, all catalysts led to total conversion
and notable high yield of 2. Next studies were performed with 10
wt% of Pd(5)/C to have a shorten reaction time.
was not total.
Furthermore, this reductive ozonolysis process (i.e. ozonolysis
and selective catalytic reduction under pressure) was applied to
other unsaturated starting material (Table 3). Methyl 10-
undecenoate gave the C-10 aldehyde ester (Table 3, Entry 2) and
95
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Green Chemistry
methyl erucate, the C-13 (Table 3, Entry 3). The yields of
aldehyde after isolation of the desired products were as good as
those from FAME of rapeseed oil. These results show that 45 methanol
ozonolysis reduction process can be applied to several FAMEs.
a result of the difference between the solubility of hydrogen in
heptane and methanol. Indeed, the solubility of hydrogen in
[
33]
m-3
-1
-3
-1
is 4.379 mol. .bar vs 1.204 mol.m .bar in n-
[
34]
heptane . Conversion of 2 in both solvent was the same but the
yield to methyl 9-hydroxynonanoate increased due to a lower
amount of mono-methyl azelaic acid formed. However, in the
presence of heptane (Table 4, Entry 5), the reaction time to obtain
4 is three time higher than in the presence of methanol, showing
that the nature of the solvent is of prime importance in this
reaction. In order to perform synthesis of 4 directly from
ozonides of FAME of rapeseed oil, the use of Pd(5)/C to carry
out reduction of 2 was studied. Compared to Raney nickel
catalyst, conversion of 2 was lower after 1.5 h (Table 4, Entry 6)
but was total only after 4 hours of reduction reaction (Table 4,
Entry 7). In these conditions, methyl 9-hydroxynonanoate was
obtained with a 93% yield.
5
Table 3 : Reductive ozonolysis process applied to several unsaturated
FAME
5
5
6
6
7
7
8
0
5
0
5
0
5
0
1
0
A
Entry
Conv. A (%)
Yield B (%)
R
n
7
1
2
3
C
C
8
H
17
17
> 99
> 99
> 99
92
93
94
H
8
8
H
11
Based on these results, the reduction of ozonides from FAME
was carried out in the presence of methanol under 50 bars of H2
at 50°C in the presence of Pd(5)/C catalyst. Conversion of
ozonides was total after 4 hours. 2 and 4 were obtained with
respectively a yield of 91% and 7%. In these conditions, methyl
azelaaldehydate was formed as main product. From this result, it
seems that the impurities are responsible of low yield of methyl
Synthesis of methyl-9-hydroxynonanoate
Methyl azelaaldehydate can be easily produced from renewable
starting material. Moreover, reduction of this aldehyde-ester
gives rise to the synthesis of methyl 9-hydroxynonanoate 4. This
alcohol-ester can be used in the polymer industry (Figure 1) to
perform bio-sourced polyester. First attempt to produce methyl 9-
hydroxynonanoate directly from ozonides of methyl oleate
without solvent (or from FAME) was carried out without success.
Only reduction into aldehyde ester 2 has been observed when
ozonide was used as starting material. We have investigated the
use of solvent in this hydrogenation step. Therefore, the catalytic
reduction of pure methyl azelaaldehydate 2 to produce methyl 9-
hydroxynonanoate 4 was performed in solvent media under 50
1
2
2
3
5
0
5
0
9
-hydroxynonanoate. The reduction of ozonides from FAME to
methyl-9-hydroxynonanoate can be performed in the presence of
Pd/C but the impurities obtained after the fisrt reduction to
methyl azelaaldehydate have to be removed from the reaction
media.
The presence of a polar solvent such as methanol is required to
obtain methyl 9-hydroxynonanoate from methyl azelaaldehydate
owing to a higher solubility of hydrogen in such solvent. In this
reaction step, the solubility of hydrogen should be high enough to
reduce the aldehyde function into alcohol. However the reaction
can not be performed directly from ozonides reduction probably
due to the presence of impurities.
bars pressure of H and at 50°C (Table 4). The reduction was first
2
performed in the presence of Pd/C, and the yield to 4 was 81%
after 4 h in n-heptane (Table 4, Entry 1). However, conversion
was not higher than 72% within this reaction time. The
conversion of 2 using Pt(5)/C (Table 4, Entry 2) was comparable
to Pd(5)/C while conversion was total with Raney nickel catalyst
in same reaction time (Table 4, Entry 3). In spite of total
conversion with nickel, the yield of methyl 9-hydroxynonanoate
was similar for all three different catalysts. In the latter case,
mono-methyl azelaic acid was formed as by-product.
Conclusions
In conclusion aldehyde-esters of various chain lengths were
prepared from unsaturated starting materials using a solvent-free
catalytic process at room temperature in the presence of
heterogeneous catalyst. The only by-products of this process are
3
5
Table 4 : Catalytic hydrogenation of 2
85 oxygen from ozone delivery and water from the reduction step.
The catalyst was removed from the reaction media by simple
filtration - and was reused at least 9 times. Simple, bifunctional
aldehyde-ester was obtained with exceptionally high purity and
may serve as intermediate in numerous polymerization steps. For
90 example, catalytic hydrogenation of aldehyde into corresponding
alcohol has been performed to obtain bifunctional alcohol-ester
monomer. Conversion of methyl azelaaldehydate was total and
yield of methyl 9-hydroxynonanoate was over 90% using Raney
nickel or Pd on activated carbon catalysts. With this global
b
a
Time
h)
Conv. 2
(%)
72
Yield 4
(%)
81
84
79
Entry
Solvent
Catalyst
(
1
2
3
4
5
Pd(5)/C
Pt(5)/C
Ni Raney
Ni Raney
Pd(5)/C
4.0
4.0
4.0
1.5
4.0
n-heptane
76
>99
>99
>99
MeOH
92
93
95
process, alcohol-ester synthesis can be carried out from
renewable feedstock in three steps with a total yield of 85%.
Moreover, all by-products are valuable.
a
b
1
0wt%, Isolated yield. Conditions: 2 (5.4 mmol), PH2 = 50 bars,
T=50°C, 30 mL.
4
0
Catalytic reduction of methyl azelaaldehydate was performed in
methanol using Raney nickel as catalyst (Table 4, Entry 4). In
these conditions, the reaction time was significantly decreased as
100
4
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Page 6 of 6
Experimental
† Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/b000000x/
6
6
0
5
Ozonolysis reaction :Ozone (O ) production was performed by
an O1-Generator (Ozone.ch) from pure oxygen gas. Mixture
O /O (1.6%, 200 mL.min ) was bubbled directly in unsaturated
3 2
starting material (10-100 g) at room temperature. Conversion of
3
‡
Footnotes should appear here. These might include comments relevant
to but not central to the matter under discussion, limited experimental and
spectral data, and crystallographic data.
-
1
5
0
5
0
5
0
5
0
5
0
1
A. Gandini, Macromolecules, 2008, 41, 9491-9504.
1
2 Y. Xia, R. C. Larock, Green Chem., 2010, 12, 1893-1909.
unsaturated compound has been followed with HPLC and
H
3
4
S. S. Narine, X. Kong, Vegetable Oils in Production of Polymers and
Plastics, Vol., John Wiley & Sons, Inc., 2005.
J. C. Ronda, G. Lligadas, M. Galià, V. Cádiz, Eur. J. Lipid Sci.
Technol., 2011, 113, 46-58.
NMR as non-destructive analysis due to the instability of 1,2,4-
trioxolanes when the temperature is over 30°C. Crude material is
directly used in reduction step without any purification.
1
1
2
2
3
3
4
4
5
70
75
5
6
Y. Xia, R. L. Quirino, R. C. Larock, J. Renewable Mater. 2013, 1, 3-27.
R. Shogren, Z. Petrovic, Z. Liu, S. Erhan, J. Polym. Environ., 2004, 12,
Reduction to aldehyde ester 2 : After elimination of O /O by
3
2
N bubbling, catalyst was carefully added to the crude materials
2
1
73-178.
obtained after ozonolysis. Hydrogen was then introduced at 25°C
7
S. Pramanik, R. Konwarh, K. Sagar, B. K. Konwar, N. Karak, Prog.
Org. Coat., 2013, 76, 689-697.
-
1
both by bubbling (200 mL.min ) and under pressure (16 bars).
The products formed were analyzed as previously described and
the conversion was determined. Crude material was filtered to
remove catalyst and purified by distillation under vacuum (90°C
at 8 mmHg) or on silica column (Petroleum Ether / Diethyl Ether
8 S. Caillol, M. Desroches, G. Boutevin, C. Loubat, R. Auvergne, B.
Boutevin, Eur. J. Lipid Sci. Technol., 2012, 114, 1447-1459.
9
1
D. P. Pfister, Y. Xia, R. C. Larock, ChemSusChem., 2011, 4, 703-717.
0 G. Lligadas, J. C. Ronda, M. Galià, V. Cádiz, J. Polym. Sci., Part A:
Polym. Chem., 2006, 44, 5630-5644.
8
8
9
9
0
5
0
5
8
5/15). Both give rise to 2 with purity up to 90%.
11 G. Lligadas, J. C. Ronda, M. Galià, V. Cádiz J. Polym. Sci., Part A:
Polym. Chem. 2006, 44, 6717-6727.
Synthesis of methyl-9-hydroxynonanoate 4: Methyl
azelaaldehydate 2 was dissolved in solvent. Catalyst was added
under stirring. The solution was heated at 50°C under dinitrogen
atmosphere. Hydrogen was then introduced under pressure (50
bars). The conversion of 2 was followed by gas chromatography
analysis without treatment while 4 has to be silylated before GC
analysis. Silylation was performed by 0.1 mL BSTFA/TMCS
1
2 L. Montero de Espinosa, J. C. Ronda, M. Galià, V. Cádiz, J. Polym.
Sci., Part A: Polym. Chem., 2008, 46, 6843-6850.
13 L. Montero de Espinosa, J. C. Ronda, M. Galià, V. Cádiz, J. Polym.
Sci., Part A: Polym. Chem., 2009, 47, 1159-1167.
14 L. M. De Espinosa, J. C. Ronda, M. Galià, V. Cádiz, J. Polym. Sci.,
Part A: Polym. Chem., 2009, 47, 4051-4063.
1
5 L. Montero de Espinosa, J. C. Ronda, M. Galià, V. Cádiz, J. Polym.
Sci., Part A: Polym. Chem., 2010, 48, 869-878.
9
9:1. Crude material was filtered to remove catalyst and purified
1
6 G. Lligadas, J. C. Ronda, M. Galià, V. Cádiz, Biomacromolecules.
on silica column (Heptane / Ethyl acetate 80/20) giving rise to 4
with high purity (>99%). Methyl 9-hydroxynonanoate can be
kept at room temperature under nitrogen flush without
degradation or polymerization.
2
006, 7, 3521-3526.
17 E. Pryde, D. Anders, H. Teeter, J. Cowan, J. Am. Oil Chem. Soc.,
961, 38, 375-379.
18 Z. S. Petrović, W. Zhang, I. Javni, Biomacromolecules, 2005, 6, 713-
19.
1
7
1
Analysis of the products : the H NMR spectra was recorded on
1
9 C. S. Fitchett, N. G. Laughton, C. G. Chappell, M. L. Khan, V.
Tverezovskiy, J. Tomkinson, P. Fowler, US 2005/0010069 A1, 2005
a Bruker Avance III Ultrashield+ 400 mHz spectrometer with
CDCl3 as solvent, and chemical shifts were given in ppm
downfield from trimethylsilane (TMS).
20 J. Yue, S. Narine, J. Am. Oil Chem. Soc., 2007, 84, 803-807.
00 21 T. S. Omonov, E. Kharraz, J. M. Curtis, J. Am. Oil Chem. Soc., 2011,
8, 689-705.
1
8
HPLC was carried out using a reversed-phase ODS, 3 µm, 2.1 x
2
2
2 R. Criegee, Angew. Chem. Int. Ed., 1975, 14, 745-752.
3 E. H. Pryde, D. E. Anders, H. M. Teeter, J. C. Cowan, J. Org. Chem.,
1960, 25, 618-621.
1
50 mm column. The mobile phase consisted of 92/8
methanol/water isocratic. The eluent flow rate was 0.25 mL/min,
and the detector was monitored at 210 nm.
Gas chromatographic analysis was performed on a Varian 3800
equipped with an HT5 column, 25m x 0.32mm x 0.25µm, and a
105 24 D. Anders, E. Pryde, J. Cowan, J. Am. Oil Chem. Soc., 1965, 42, 236-
43.
2
2
2
2
5 H. Edwards, Lipids, 1966, 1, 1-5.
6 O. Lorenz, C. R. Parks, J. Org. Chem., 1965, 30, 1976-1981.
7 O. Privett, C. Nickell, J. Am. Oil Chem. Soc., 1962, 39, 414-419.
-
1
nitrogen flow of 1 mL.min . A split/splitless injector (1%) was
heated at 250°C. For each injection, 0.1 µL of solution to analyze 110 28 O. S. Privett, E. C. Nickell, J. Lipid Res., 1963, 4, 208-211.
9 E. Nickell, O. Privett, Lipids, 1966, 1, 166-170.
30 M. Sasaoka, D. Suzuki, T. Shiroi, US 5770729, 1998
2
was used. FID detector was heated to 350°C using air and
hydrogen flow respectively of 300- and 30 mL.min .
-
1
3
3
1 Y. S. Hon, K. C. Wu, Tetrahedron, 2003, 59, 493-498.
2 S. Ramachandran, P. V. Rao, D. G. Cornwell, J. Lipid Res., 1968, 9,
137-139.
3 K. Radhakrishnan, P. A. Ramachandran, P. H. Brahme, R. V.
Chaudhari, J. Chem. Eng. Data, 1983, 28, 1-4.
Acknowledgements
1
1
1
15
20
25
3
3
We are grateful to the French National Research Agency for the
financial support for the project ANR-GUI-AAP-03.
4 S. K. Lachowicz, D. M. Newitt, K. E. Weale, Transactions of the
Faraday Society, 1955, 51, 1198-1205.
Notes and references
a
Université de Poitiers - IC2MP- UMR CNRS 7285, 4, rue Michel
Brunet, 86022 Poitiers Cedex, France. Tel : +33 5 49 45 39 51
E-mail: yannick.pouilloux@univ-poitiers.fr , karine.vigier@univ-
poitiers.fr
5
5
b
ARKEMA FRANCE, Rue Henri Moissan, 69493 Pierre-Bénite, France.
c
ARKEMA FRANCE, 420 Rue d'Estienne d'Orves, 92705 Colombes,
France
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