Polyamide precursors from renewable 10-undecenenitrile and methyl acrylate via olefin cross-metathesis

Article abstract of DOI:10.1039/c2gc35648a

The ruthenium-catalyzed cross-metathesis of the unsaturated fatty acid derivative 10-undecenenitrile 1 arising from castor oil with methyl acrylate produces a C12 nitrile ester with high turnover number. This product has potential as a new bio-sourced intermediate for the production of polyamides. This route competes favourably with the reverse cross-metathesis of methyl 10-undecenoate with acrylonitrile leading to the same C12 α,ω-amino ester 7 after hydrogenation of the carbon-carbon double bond and the nitrile functionality.

Full text of DOI:10.1039/c2gc35648a

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PAPER
Polyamide precursors from renewable 10-undecenenitrile and methyl acrylate
via olefin cross-metathesis†
X. Miao,a C. Fischmeister,a P. H. Dixneuf,a C. Bruneau,a J.-L. Duboisb and J.-L. Couturierc
Received 27th April 2012, Accepted 25th May 2012
DOI: 10.1039/c2gc35648a
The ruthenium-catalyzed cross-metathesis of the unsaturated fatty acid derivative 10-undecenenitrile 1
arising from castor oil with methyl acrylate produces a C12 nitrile ester with high turnover number. This
product has potential as a new bio-sourced intermediate for the production of polyamides. This route
competes favourably with the reverse cross-metathesis of methyl 10-undecenoate with acrylonitrile
leading to the same C12 α,ω-amino ester 7 after hydrogenation of the carbon–carbon double bond and the
nitrile functionality.
Introduction
In the context of petrochemical resources shortage,1 among
renewable carbon sources, fats and oils present a strong potential
for a variety of applications depending on the control of selective
catalytic transformation reactions and have already received
much attention.2,3
10-Undecylenic acid derivatives constitute valuable feedstock
readily available from castor oil.4 These renewable compounds
have already been used for the industrial production of C11-
polyamide (PA11) in the Rilsan® process.5 They have also a
huge potential for the generation of C12-amino esters, the pre-
cursors of C12-polyamide, upon cross-metathesis with functional
olefins. Catalytic olefin metathesis is a powerful tool in organic
chemistry6 and polymer synthesis.7 In particular, the cross-
metathesis reaction has opened up efficient routes for the for-
mation of new CvC bonds under mild conditions to readily
give higher value to simple synthetic intermediates,8 or to intro-
duce a desired functionality into complex architectures.9 The
introduction of a polar functionality into unsaturated fatty acid
derivatives, by cross-metathesis with alkynes10 or electron poor
olefins, such as acrylates,11 or even allyl chloride,12 leading to
end-functionalized long chain alkenes, is now possible thanks to
the development of very active and functional group tolerant
catalysts.13
Scheme 1 Syntheses of methyl 12-aminododecanoate 7.
We now report that the linear C12 α,ω-amino ester 7, the same
polyamide precursor, can be prepared via cross-metathesis of
methyl acrylate with the bio-sourced 10-undecenenitrile 1 in the
presence of ruthenium-alkylidene catalysts (Scheme 1, route
(b)).17
We show that the second generation Hoveyda type catalysts
are the most efficient for these transformations. The reactions are
drastically improved by slow addition of the catalyst to reach
high TON in linear nitrile esters.
Acrylonitrile is not a very reactive partner in olefin metathesis
reactions,14 however the cross-metathesis of methyl 10-unde-
cenoate with acrylonitrile offers sustainable catalytic access to
the precursor of C12-polyamide 7 (Scheme 1, route (a)).15,16
Results and discussion
Cross-metathesis reaction
Cross-metathesis of acrylates with fatty ester derivatives was first
investigated with methyl oleate as partner.12 Meier showed that
99% conversion of the oleate into the cross-metathesis products
was obtained with second generation Grubbs (I) and Hoveyda–
Grubbs (II) catalysts. The metathesis with catalyst II could be
performed with an excess of acrylate and no additional solvent,
indicating that the catalyst was not inhibited by the acrylate.11
Cross-metathesis of methyl acrylate was extended to methyl
aUMR6226-CNRS-Université de Rennes 1, Institut des Sciences
Chimiques de Rennes, Campus de Beaulieu, 35042 Rennes cedex,
France. E-mail: christian.bruneau@univ-rennes1.fr
bARKEMA, 420 Rue d’Estienne d’Orves, 92705 Colombes, France
cARKEMA, CRRA, BP 63 Rue Henri Moissan, 69493 Pierre Bénite,
France
†Electronic supplementary information (ESI) available: Characterization
data and experimental procedures. See DOI: 10.1039/c2gc35648a
This journal is © The Royal Society of Chemistry 2012
Green Chem., 2012, 14, 2179–2183 | 2179

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ricinoleate,11d,15a methyl erucate and methyl petroselinate,11b
and also to oleyl alcohol and acetate in solvent free
conditions.11a
(Table 1, entries 2, 4, 6) and even at room temperature (Table 1,
entries 3, 5, 7), leading to complete conversion and high yield of
the desired product 3. The cross-metathesis reaction took place
with high stereoselectivity in favour of the E isomer.
Methyl undecenoate is obtained by thermal cleavage of
methyl ricinoleate at high temperature. 10-Undecenoic acid
arises from hydrolysis of the ester and provides a variety of 10-
undecylenic acid derivatives, including the corresponding nitrile.
Cross-metathesis of methyl acrylate and other electron deficient
olefins with methyl 10-undecenoate15a,18 and 10-undecylenic
aldehyde19 has been efficiently achieved with catalyst II in order
to produce α,ω-bifunctional derivatives. The advantage of using
10-undecenenitrile, another biosourced substrate obtained upon
ammoxidation20 of 10-undecenoic acid, as a potential source of
amine has never been evaluated. The cross-metathesis with
methyl acrylate was thus investigated with the objective of pro-
ducing compound 3 and then the amino ester 7, under optimized
conditions.
Based on our previous studies on cross-metathesis transform-
ations of fatty derivatives, the second generation ruthenium com-
plexes I–IV21 were investigated (Scheme 2).
Our first attempts were carried out with 2 equivalents of acry-
late in toluene in the presence of 0.5 mol% of catalyst
(Scheme 1, route (b)). Catalyst I appeared to be less efficient as
the conversion was not completed after 19 h at 50 °C (Table 1,
entry 1). The catalysts II, III and IV bearing a chelating benzyli-
dene ligand were very efficient at temperatures as low as 50 °C
As it was previously shown that cross-metathesis of acrylate
could be carried out without a solvent, cross-metathesis of 10-
undecenenitrile in neat methyl acrylate as the solvent was tested.
The metathesis reaction took place using 1 mol% of catalyst II
and 2 equivalents of acrylate and led to 64% conversion of 1 and
41% isolated yield of 3 – due to the competitive self-metathesis
reaction of 1 – after 22 h of reaction at 50 °C (Table 2, entry 1).
When the temperature was increased to 100 °C, the reaction
efficiency was enhanced (85% conversion, 74% isolated yield of
3 – Table 2, entry 4).
Increasing the amount of methyl acrylate under otherwise
identical conditions improved the efficiency and allowed the
reaction to reach 85% conversion of 1 with 78% yield of 3 in the
presence of 20 equivalents of acrylate (Table 2, entry 5). Lower
catalyst loadings resulted in lower conversions. For comparison,
the reaction of methyl 10-undecenoate with methyl acrylate (10
equivalents – bulk conditions) in the presence of 0.1 mol% of
catalyst II gave 99% of the expected unsaturated C12-diester at
50 °C after 3 h reaction time. This result compared with the data
of Table 2, entry 4 reveals that the nitrile functionality has a
negative effect on the metathesis reaction as compared to the
ester.
To improve the TON values while maintaining high conver-
sion, we investigated the slow addition of the catalyst into the
reaction mixture. This technique can drastically improve the
efficiency of catalytic reactions when the lifetime of the catalytic
species is short, and was successfully used in the cross-metath-
esis with acrylonitrile15a (Scheme 1 – route (a)). The results are
gathered in Table 3. Catalyst II was dissolved in toluene and
slowly injected with a syringe pump apparatus (dropwise
addition) in order to ensure a reliable continuous addition of the
catalyst into the reaction mixture. The catalyst solution was
added within 2 h 40 min and the reaction mixture was main-
tained at the desired temperature until a total time of 5 h. With a
catalyst loading of 0.05 mol%, the temperature could be
decreased down to 50 °C to ensure a TON close to 2000 with
almost complete conversion (Table 3, entries 1–2). At 25 °C, the
reaction was too slow and a conversion of only 42% could be
obtained (Table 3, entry 3). With lower catalyst loadings, a
higher temperature of 100 °C had to be applied to reach satisfac-
tory conversion. With 0.01 mol% catalyst loading, 92% conver-
sion of 1 leading to 3 with high selectivity toward the cross-
Scheme 2 Ruthenium-based olefin metathesis catalysts.
Table 1 Cross-metathesis of 10-undecenenitrile with methyl acrylatea
Entry Cat. T (°C) t (h) Conv.b (%) Yieldb (%) E/Z ratiob
Table 2 Cross-metathesis of 10-undecenenitrile with methyl acrylate
in bulk conditionsa
1
2
3
4
5
6
7
I
II
II
III
III
IV
IV
50
50
25
50
25
50
25
19
1
2
2
2
1
1
64
99
99
99
97
99
99
51
99c
99
98
95
99
96
9.4
13.3
12.8
12.7
14.2
8.9
Entry 2 (equiv.) T (°C) t (h) Conv.b (%) Yieldb (%) E/Zb
1
2
3
4
5
2
5
10
10
20
50
50
50
100
50
22
19
23
23
20
64
72
79
85
85
41
63
73
74
78
12.7
7.3
9.5
10.3
11.7
9.7
a 1 (0.5 mmol), [1] = 0.05 M, 2 (1 mmol), catalyst (0.0025 mmol,
0.5 mol%), toluene (10 ml). b Determined by GC using dodecane as an
internal standard. c Isolated yield = 98%.
a 1 (3 mmol), catalyst II (1 mol%), open system. b Determined by GC
using dodecane as an internal standard.
2180 | Green Chem., 2012, 14, 2179–2183
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Table 3 Cross-metathesis of 1 with methyl acrylate using slow addition of catalysta
Entry
Cat. (mol%)
T (°C)
Conv.b (%)
Yieldb (%)
E/Zb
TONc
STONc
1
2
3
4
0.05
0.05
0.05
0.025
0.01
0.0075
0.0075
0.005
0.005
100
50
25
100
100
100
100
100
100
98
96
42
98
92
80
91
73
86
98e
96
36
98
92f
66
80
61
63
8.3
13.4
11.2
9.5
8.1
7.1
8.2
6.6
7.9
1960
1920
840
3920
1960
1920
720
3920
9200
8800
10 667
12 200
12 600
5
9200
6
10 667
12 133
14 600
17 200
7d
8
9d
a 1 (2 mmol), 2 (8 mmol), toluene (38 ml), [1] = 0.05 M, catalyst II was dissolved in toluene (2 ml), added in 2 h 40 min, then the reaction mixture
was maintained at the desired temperature until a reaction time of 5 h. b Determined by GC using dodecane as an internal standard. c TON: conv. of
1/cat. loading; selective TON (STON): GC yield of 3/cat. loading. d [1] = 0.5 M. e Isolated yield: 97%. f Isolated yield: 90%.
metathesis product (92% yield) provided a TON of 9200
(Table 3, entry 5).
compound 6, another precursor of the amino ester 7 (Scheme 1,
route (a)), was obtained with a highest TON of 1900 using
0.05 mol% of catalyst II,15a thus demonstrating (i) the superior-
ity of the herein reported pathway for the synthesis of 7
(Scheme 1, route (b) > route (a)) and (ii) the inhibiting character
of acrylonitrile in cross-metathesis transformations.
When the catalyst loading was decreased below 0.01 mol%,
10-undecenenitrile was not completely consumed within 5 h and
the lower the catalyst loading the lower the conversion (Table 3,
entries 6, 8). However, the conversions were improved when the
concentration of the substrate was increased from 0.05 M to 0.5
M (entries 6–9). It is noteworthy that below 0.01 mol% catalyst
loading, the selective TONs (STONs), indicators of the conver-
sion into the desired product 3, were significantly lower than the
TONs based on the conversion of 1, which revealed the presence
of byproducts. Finally, the best STON (12 600) was obtained at
100 °C in the presence of 0.005 mol% of catalyst II with the
slow addition technique. The E isomer was still formed as the
major product.
In order to understand this evolution of the reaction and ident-
ify the byproducts, the reaction profile of the metathesis reaction
was monitored under the reaction conditions depicted in Table 3
entry 7 (Fig. 1 – [1] = 0.5 M; II: 0.0075 mol%, 100 °C) and
entry 9 (Fig. 2 – [1] = 0.5 M; II: 0.005 mol%, 100 °C).
Fig. 1 Cross-metathesis of 1 with methyl acrylate. [1] = 0.5 M; II:
0.0075 mol%, 100 °C. Conversion vs. internal standard. 1/3/8: GC ratio.
In both cases, a short induction period of about 15 min was
detected before the reaction started. As soon as the cross-metath-
esis with methyl acrylate was initiated, the self-metathesis of 10-
undecenenitrile 1 giving the corresponding symmetrical unsatu-
rated C20-dinitrile 8 (Scheme 3) started at a comparable rate.
With low catalyst loading (0.005 mol%) the self-metathesis
product 8 can reach up to 34% after 110 min, whereas a
maximum of 22% is obtained after 75 min with 0.0075 mol%
catalyst loading. It can be noted that the maximum values for the
formation of 8 are obtained when the same amounts of catalyst
(0.007 mmol) are added and the consumption of 10-undeceneni-
trile is around 75%. Then, part of the self-metathesis product 8 is
consumed by cross-metathesis with methyl acrylate, but not
completely and the evolution of the metathesis transformations is
stabilized around 200 min, after complete injection of the cata-
lyst at 160 min. Consequently, the yield of 3 is higher starting
from 0.0075 (80%) than from 0.005 mol% (63%) catalyst
loading. Higher concentration of the catalyst is necessary to
ensure high selectivity that is cross-metathesis rather than self-
metathesis. This is illustrated in Table 3 where the GC yields are
close to the conversions when the amount of catalyst is higher
than 0.01 mol% and then the gap between these 2 numbers
increases when the catalyst loading decreases. For comparison,
Fig. 2 Cross-metathesis of 1 with methyl acrylate. [1] = 0.5 M; II:
0.005 mol%, 100 °C. Conversion vs. internal standard. 1/3/8: GC ratio.
Scheme 3 Self metathesis of 10-undecenenitrile.
Green Chem., 2012, 14, 2179–2183 | 2181
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Tandem cross-metathesis/CvC and CN hydrogenation
entry 2). On the other hand, when the metathesis reaction took
place at room temperature, 95% yield of 7 was obtained with
only 20 mol% of base (Table 4, entry 5) and the yield reached
The ruthenium residues arising from olefin metathesis are known
to catalyze hydrogenation of carbon–carbon double bonds result-
ing from olefin ring closing and cross-metathesis.22
We have also shown that the tandem cross-metathesis/hydro-
genation sequence could be adapted to the hydrogenation of
unsaturated fatty derivatives.19 For example, under 10 bar of
hydrogen pressure at 50 °C for 24 h, 6 obtained upon cross-
metathesis of 4 and 5 in the presence of 0.5 mol% of catalyst II
(Scheme 1, route (a)) quantitatively led to the saturated C12
nitrile ester, which was isolated in 91% yield.
t
97% with 30 mol% of BuOK. In the latter case the amino ester
7 was isolated in 90% yield and no trace of secondary amine
could be detected, thus demonstrating the high selectivity of the
catalytic system.25
Conclusion
We have shown that the cross-metathesis of 10-undecenenitrile
with methyl acrylate takes place very efficiently with the
Grubbs–Hoveyda second generation catalyst. The best pro-
ductivity is obtained using continuous injection of the catalyst
into the reaction mixture at 100 °C. Under these conditions a
turnover number of 17 200 at 86% conversion of the fatty nitrile
is obtained. Hydrogenation of the carbon–carbon double bond
and the nitrile functionality in the presence of the ruthenium cat-
alyst residue gives access to the C12 amino ester, the precursor
of polyamide. This reaction takes place in the presence of
tBuOK as a base under 20 bar of hydrogen at 80 °C. This pro-
cedure (Scheme 1, route (b)) is more favorable than the one start-
ing from methyl 10-undecenoate and acrylonitrile, which allows
one to obtain a maximum turnover number of 1900 at 95% con-
version of the fatty ester during the metathesis step.15a This
overall tandem procedure provides a sustainable route to linear
amino esters, useful polyamide precursors, as a single catalyst is
introduced from the outset of the process to perform 3 catalytic
transformations (cross-metathesis, carbon–carbon double bond
hydrogenation and nitrile reduction) from methyl acrylate and
undecenenitrile, 2 biosourced substrates.
In order to produce the desired amino ester from 1 and 2, we
directly investigated the tandem cross-metathesis/hydrogenation
t
in the presence of BuOK (Scheme 4), which has recently been
shown to generate efficient nitrile reduction catalytic systems in
the presence of olefin metathesis residue.23,24 The results shown
in Table 4 indicate that both the amount of base and catalyst
loading are important parameters. The nitrile hydrogenation
could not be achieved with the very low 0.05 mol% catalyst
loading used for the cross-metathesis reaction. When the meta-
thesis reaction was performed at 100 °C the conversion into 3
was completed within 1 h and the same efficiency was obtained
at room temperature with catalyst loadings of 1 and 3 mol%.
Whatever the metathesis temperature applied during the first
step, at 1 mol% catalyst loading, hydrogenation under 20 bar of
hydrogen at 80 °C led to complete conversion into the saturated
nitrile ester 9 (Table 4, entries 1 and 4). It is also noteworthy that
full conversion into the saturated amino ester 7 was obtained
t
only in the presence of a high amount of BuOK and 3 mol% of
catalyst loading in the metathesis step (Table 4, entries 3, 5, 6).
When the metathesis step was carried out at 100 °C, 30 mol% of
tBuOK were necessary to reach 96% yield of 7, whereas with
15 mol% of base a mixture of 7 and 9 was obtained (Table 4,
Acknowledgements
The authors are grateful to Arkema for a PhD position to XM, to
CNRS and the French Ministry of Research, and to the European
Network IDECAT (NOENMP3-CT-2005-011730) for support.
The authors also wish to thank Umicore Company for fruitful
discussions.
Notes and references
Scheme 4 Sequential cross metathesis/hydrogenation.
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1
2
3
4
5
6
1
3
3
1
3
3
100
100
100
r.t.
r.t.
r.t.
30
15
30
30
20
30
40
40
40
40
40
40
97
43
—
96
—
—
—
50
96
—
95
97
a 1 (0.5 mmol), 2 (1 mmol), toluene (10 ml), metathesis reaction: 1 h,
complete conversion into 3, hydrogenation reaction under 20 bar of
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yield.
2182 | Green Chem., 2012, 14, 2179–2183
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