Ruthenium-alkylidene catalysed cross-metathesis of fatty acid derivatives with acrylonitrile and methyl acrylate: A key step toward long-chain bifunctional and amino acid compounds

Article abstract of DOI:10.1039/c1gc15569e

The ruthenium catalysed cross-metathesis of fatty-esters arising from plant oils with acrylonitrile is presented. The resulting linear nitrile ester products have potential as new intermediates for polyamides synthesis. A series of commercially available catalysts are able to promote the transformation of methyl 10-undecenoate 1, dimethyl octadec-9-en-1,18-dioate 5 and methyl ricinoleate 9 with acrylonitrile and a protocol based on the slow addition of catalyst allowed TONs as high as 1900 (92% yield) to be reached for cross-metathesis with acrylonitrile. These cross-metathesis conditions have been applied to methyl acrylate and TONs up to 7600 were obtained.

Full text of DOI:10.1039/c1gc15569e

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PAPER
Ruthenium–alkylidene catalysed cross-metathesis of fatty acid derivatives
with acrylonitrile and methyl acrylate: a key step toward long-chain
bifunctional and amino acid compounds†
X. Miao, R. Malacea, C. Fischmeister,* C. Bruneau* and P. H. Dixneuf
Received 17th May 2011, Accepted 18th July 2011
DOI: 10.1039/c1gc15569e
The ruthenium catalysed cross-metathesis of fatty-esters arising from plant oils with acrylonitrile
is presented. The resulting linear nitrile ester products have potential as new intermediates for
polyamides synthesis. A series of commercially available catalysts are able to promote the
transformation of methyl 10-undecenoate 1, dimethyl octadec-9-en-1,18-dioate 5 and methyl
ricinoleate 9 with acrylonitrile and a protocol based on the slow addition of catalyst allowed
TONs as high as 1900 (92% yield) to be reached for cross-metathesis with acrylonitrile. These
cross-metathesis conditions have been applied to methyl acrylate and TONs up to 7600 were
obtained.
even allyl chloride,11d leading to end-functionalized long chain
Introduction
alkenes, is now possible.
Catalytic olefin metathesis is a powerful tool in organic
Although several examples of cross-metathesis of acrylonitrile
chemistry1 and polymer synthesis.2 In particular, the cross-
with organic substrates have been reported,12 including that of
metathesis reaction has opened new strategies for the efficient
a few long-chain molecules,13 the cross-metathesis of fatty acid
formation of new C–C bonds under mild conditions to readily
derivatives with acrylonitrile has only recently been performed.14
give higher value to simple synthetic intermediates,3 or to intro-
The later reaction constitutes a strategic way to generate
duce a desired functionality into complex architectures.4 Cross-
linear amino acid derivatives, and thus their polyamides,15 from
metathesis also contributes to develop green processes and
offers a strong potential for the transformation of unsaturated
renewable materials.5
renewable resources, via a,w-unsaturated cyano esters arising
from the initial cross-metathesis reaction (Scheme 1). Moreover,
acrylonitrile has recently become a sustainable raw material as it
is produced from glycerol by dehydration into acrolein followed
The search for renewable carbon sources is a domain of strong
economical and environmental interest in a context of petrol
by ammoxidation.16
resource shortage.6 However, the shift from petrochemical based
Here we report the study of the cross-metathesis of several
to bio-sourced compounds requires the preliminary discovery
fatty acid derivatives with acrylonitrile using a variety of
of new, efficient molecule combination processes and their
ruthenium-alkylidene alkene metathesis catalysts. We show that
adaptation to the large scale production of useful compounds.
the second generation Hoveyda type catalysts are the most
Among renewable carbon sources, fats and oils do present a
efficient for these transformations. The reactions are drastically
strong potential for a variety of applications depending on the
improved by slow addition of the catalyst to reach high TON
control of selective catalytic transformation reactions. They have
already received much attention.7,8
Thanks to the development of very active and functional
group tolerant ruthenium catalysts,9 the introduction of a polar
functionality into fatty acid derivatives, by cross-metathesis
with alkynes10 or electron poor olefins, such as acrylates,11a–c or
in linear nitrile esters. We also show improvement for the cross-
metathesis of methyl acrylate with fatty acid derivatives.
Results and Discussion
Olefin metathesis was shown to be a method of choice for the
transformation of fat and oil derivatives.17 Early works have
focused on the transformation of fatty acids or esters by self-
metathesis18 or cross-metathesis19 with small molecules, such as
UMR 6226-CNRS-Universite´ de Rennes 1 Sciences Chimiques de
Rennes, Catalyse et Organome´talliques, Campus de Beaulieu, 35042,
ethylene (ethenolysis), for the production of raw materials of
interest for the synthesis of polymers. Efficient cross-metathesis
reactions of acrylonitrile with fatty acid derivatives are a key step
toward the sustainable production of polyamide monomers. A
Rennes cedex, France. E-mail: cedric.fischmeister@univ-rennes1.fr,
christian.bruneau@univ-rennes1.fr
† Electronic supplementary information (ESI) available: Characterisa-
tion data and experimental procedures. See DOI: 10.1039/c1gc15569e
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Scheme 1 The synthesis of amino acids or esters from renewable fatty compounds.
preliminary study14 on the cross-metathesis of acrylonitrile with
Table 1 Cross-metathesis of methyl 10-undecenoate
acrylonitrilea
1
with
unsaturated fatty acid derivatives revealed the higher efficiency
of the 2nd generation Hoveyda catalyst A20 with respect to
the second generation Grubbs catalyst21 and the ruthenium
indenylidene catalyst F (Fig. 1).22 However, modest TON were
obtained in this study. We have now evaluated several other
catalysts for their stability with acrylonitrile and their efficiency
for cross-metathesis with high TONs. Thus in addition to
catalyst A, other Hoveyda and Grubbs type catalysts, B,23 C,23
Acrylonitrile
Entry Catalyst (equiv.)
Conv. (%)b Yield (%)b
Z/Ec
1
2
3
4
5
6
A
A
A
B
C
D
1
2
3
2
2
2
86 (94)d
96
—
96
—
80
—
81
—
3.2/1
—
4.1/1
4.9/1
3.5/1
95d
80
9
81
D,24 as well as indenylidene complexes E,25 F,22 G,26
H
27 (Fig. 1)
a 1 (0.5 mmol, [ ] = 0.05 M), catalyst (1 mol%), toluene (10 ml), 80 ◦C, 1 h.
b Determined by GC using dodecane as internal standard. c Determined
by GC. d 4 h.
were first evaluated on the cross-metathesis of acrylonitrile with
methyl-10-undecenoate 1 (Scheme 2) and dimethyl octadec-9-
en-1,18-dioate 5.
1
Cross-metathesis of methyl 10-undecenoate 1 with
acrylonitrile concentration inhibits catalyst activity (94% and
95% conversion after 4 h, respectively)(Table 1, entries 1–3).
The cross-metathesis of undecylenic ester 1 was then performed
in toluene at 80 ◦C using 2 equivalents of acrylonitrile and
1 mol% of catalysts A, B, C, and D (Scheme 2).
Among the active catalysts, Hoveyda catalyst A was found to
be the most efficient, allowing 96% conversion in 1 h (Table 1,
entry 2). The less sterically hindered Hoveyda type complex
B exhibited high activity whereas the thermally less robust
Grubbs type catalyst C was found to be almost inefficient
to promote the reaction (Table 1, entries 4, 5). Under the
same conditions, complex D, also featuring Hoveyda type
architecture, displayed an efficiency similar to that of B. It
acrylonitrile. Catalysts and factors of influence
Undecylenic acid and ester are valuable renewable compounds
readily obtained from castor oil.28 These renewable compounds
have already been used for the industrial production of C11-
29
R
polyamide in the Rilsanꢀ process. The cross-metathesis of
methyl 10-undecenoate 1 with acrylonitrile has the potential
to offer catalytic access to the precursor of C12-polyamide
2. Initial investigations of this catalytic reaction (Scheme 2)
with catalyst A showed that no more than 2 equivalents of
acrylonitrile were necessary to ensure an optimal transformation
(96% conversion after 1h). Both lower and higher amounts of
acrylonitrile resulted in slower reactions, suggesting that high
Fig. 1 Ruthenium based olefin metathesis catalysts.
Scheme 2 Cross-metathesis of ester 1 with acrylonitrile.
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Table 2 Cross-metathesis of methyl 10-undecenoate 1 with acrylonitrilea
Entry
[1] (mol L-1)
0.05
Cat. A (mol%)
T/◦C
80
t (h)
Conv. (%)b
Yields (%)b
Z/Ec
1
2
3
4
1
1
2
1
2
1
2
3.5
24
19
15
24
95
96
97
98
95
96
90
93
81
94
87
3.3/1
3.2/1
2.8/1
2.8/1
1.7/1
1.7/1
3.0/1
3.3/1
3.4/1
3.6/1
3.6/1
96
98
96
0.1
1
80
0.25
1
80
0.05
0.5
80
93
80
93
87
5
6
7
0.05
0.05
0.05
0.2
1
0.5
80
60
60
a 1 (0.5 mmol), acrylonitrile (1 mmol, 2 equiv.), A (0.2–1 mol%), toluene (2–10 ml). b Determined by GC using dodecane as internal standard.
c Determined by GC.
thus appears that PCy3 releasing catalyst precursor C, as a
Grubbs II type catalyst,14 does not tolerate acrylonitrile or its
cross-metathesis intermediate. As generally observed in cross-
metathesis reactions with acrylonitrile, the stereoselectivity was
in all cases in favor of the Z isomer.12a,b
distillation19j or chromatography through activated alumina.19d,e
However, for large scale processes these purifications are costly
in terms of energy consumption and waste production. For these
reasons we turned our attention to another strategy based on
slow addition of catalyst.
The transformation of ester 1 with catalyst A was then
investigated in more detail with the aim to reach higher TONs. In
particular, the effect of concentration, temperature and catalyst
loading were evaluated (Table 2). The efficiency of the transfor-
mation was not affected by increasing the concentration of 1 to
0.25 M (Table 2, entries 1–3). In contrast, the stereoselectivity
was more sensitive to concentration variations and slightly
decreased when the concentration of 1 increased. Of note, in each
case the Z/E ratio remained unchanged upon extended reaction
time, suggesting that no secondary metathesis took place during
the reactions. It is worth noting that high conversions were still
reached with a catalyst loading as low as 0.2 mol% (Table 2,
entry 5) and at 60 ◦C with 0.5 mol% of A (Table 2, entries 6, 7).
In order to maintain a high conversion (>90%), catalyst A
loading could not be lowered below 0.5 mol% (TON = 186, Table
2, entries 4, 5). To further decrease the catalyst loading, typical
strategies consist in the ultra purification of the reagents by
As depicted in Table 2, all reactions were not improved to
a large extent by using long reaction times. This observation
was attributed to a rapid decomposition of the ruthenium
(pre)catalyst and/or the ruthenium methylidene catalyst under
the reaction conditions. To confirm this assumption, diethyl
diallylmalonate, a benchmark RCM substrate that can be easily
ring-closed by 2nd generation Grubbs–Hoveyda metathesis cat-
alysts, was added to a reaction mixture after 2 h. No conversion
was observed after 1 h at room temperature, indicating that
no metathesis catalyst was present in the reaction mixture.
Consequently, the slow addition of the catalyst was envisioned
to circumvent this problem and improve the TON values
while maintaining high conversions. Under classical conditions,
hereafter called single dose addition, a Schlenk tube was loaded
with reactants, catalyst A (0.2 mol%) and 10 ml of toluene. As
depicted in Table 3 (entries 1 and 2) the conversion dropped to
a poor 61% when the catalyst loading was reduced to 0.1 mol%.
Table 3 Influence of the catalyst addition mode on the cross-metathesis of 1 with acrylonitrilea
Entry
Cat. (mol%)
Addition mode
Solvent (ml)
[1] (mol L-1)
t (h)
Conv. (%)b
Z/Ec
TON
1
2
3
4
A (0.2)
Single dose
Single dose
Batchwised
Batchwise
Dropwisef
Dropwisef
Dropwisef
Dropwisef
Dropwisef
Dropwisef
Dropwisef
Dropwisef
Dropwisef
Dropwisef
Dropwisef
10
10
0.05
0.05
19
18
5
5
5
5
5
5
5
5
5
5
5
5
5
81
61
94
3.4/1
3.9/1
3.0/1
3.9/1
3.0/1
3.1/1
2.9/1
3.8/1
4.0/1
3.9/1
3.5/1
n.d.
405
610
470
750
940
960
1900
1780
1140
2280
1340
—
A (0.1)
A (0.2)
8 + 4 ¥ 0.5
8 + 4 ¥ 0.5
8 + 2
8 + 2
8 + 2
4 + 1
1 + 1
8 + 2
8 + 2
8 + 2
8 + 2
8 + 2
8 + 2
0.0625/0.05e
0.0625/0.05e
0.0625/0.05e
0.0625/0.05e
0.0625/0.05e
0.125/0.1e
0.5/0.25e
A (0.1)
75 (73)g
94
5
A (0.1)
6h
A (0.1)
96
7h
A (0.05)
A (0.05)
A (0.05)
A (0.025)
D (0.05)
E (0.05)
F (0.05)
G (0.05)
H (0.05)
95 (92)g
89 (87)b
57 (41)b
55
8h
9h
10h
11h
12h
13h
14h
15h
0.0625/0.05e
0.0625/0.05e
0.0625/0.05e
0.0625/0.05e
0.0625/0.05e
0.0625/0.05e
67
0
16
0
n.d.
n.d.
n.d.
320
—
240
12
a 1 (0.5 mmol), acrylonitrile (1 mmol, 2 equiv.), toluene, 80 ◦C. b Determined by GC using dodecane as internal standard. c Determined by GC.
d Catalyst A in 2 ml of toluene was added in 4 equal portions (0.5 ml) at t = 0, 1 h, 2 h, 4 h. e Initial [1]/final [1]. f Catalyst A in 2 ml of toluene was
continuously added into the reaction mixture using a syringe pump. Addition time = 160 min. g Isolated yield. h 100 ◦C.
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First, the catalyst was added in small portions during the
reaction (batchwise addition). Catalyst A (0.2 mol%) dissolved
in 2 ml of toluene was thus added in 4 equal portions into a
Schlenk tube containing the reactants and 8 ml of toluene.30
This method resulted in a slight improvement of the reaction
productivity from a TON of 405 (Table 3, entry 1) to a TON
of 470 when using a catalyst loading of 0.2 mol% (Table 3,
entry 3) and 750 with 0.1 mol% of catalyst but in that case the
conversion dropped to 75% (Table 3, entry 4). As depicted in
Table 3, the stereoselectivity was not strongly affected by the
catalyst addition mode.
Although the TON improvement from 405 to 470 (Table 3,
entries 1, 3) was quite modest, the reaction profile obtained
with a batchwise addition of catalyst clearly indicated that lower
catalyst loading should be possible. Indeed, as shown in Fig. 2,
the conversion determined from reaction samples reached 74%
after 2 h when only 50% of the catalyst had been added and 90%
before the last addition of catalyst.
This tendency may result from the higher thermal stability of
Hoveyda type catalysts but also from different initiation modes
of these two types of catalysts, as recently reported by Plenio.31
Furthermore, by contrast with recently reported data on RCM
reactions,31,32 an increase of the substrate concentration led to
lower conversions when low catalyst loading were used (Table
3, entries 7–9). These results clearly show the peculiarity of
acrylonitrile in cross-metathesis transformations.
The reaction profile monitored under the reaction conditions
depicted in Table 3, entry 7 revealed several key features of this
transformation (Fig. 3). First, a long induction period of 30 min
was necessary before the reaction started. This induction period
may result from the inhibition by acrylonitrile of the catalyst
activation and at very low catalyst concentration, it may also
result from the neutralisation of inhibiting impurities by the
catalyst, the reaction would only start once these impurities
have been eliminated. It was also observed that during the
reaction, besides the cross-metathesis with acrylonitrile, the self-
metathesis of 1 resulting in the diester 3 occurred to a low extent
(Scheme 2). However, once formed, compound 3 reacted with
acrylonitrile producing the desired compound 2.
Fig. 2 Conversion of 1 vs. time for the cross-metathesis with acryloni-
trile performed at 80 ◦C in toluene with a batchwise addition of catalyst.
0.05 mol% of catalyst A added at t = 0, 1 h, 2 h, 4 h (0.2 mol% of A
in total). Conversions at 2 h and 4 h were measured on a sample taken
before addition of catalyst.
Fig. 3 Kinetic study for the cross-metathesis reaction of 1 with 2 equiv.
of acrylonitrile using 0.05 mol% of catalyst A at 100 ◦C with catalyst
added over a period of 160 min.
Based on this result, lower catalyst loadings were then
attempted at 100 ◦C using a syringe pump apparatus (dropwise
addition) in order to ensure a reliable continuous addition of
the catalyst into the reaction mixture. This process constituted a
real breakthrough since it was possible to decrease the catalyst
loading down to 0.05 mol% while maintaining a high conversion
(96%) thus leading to a TON of 1900 (Table 3, entry 7). The
TON could be slightly increased to 2280 using a lower catalyst
loading but the conversion dropped to only 55% (Table 3,
entry 10). However, this slight improvement should not balance
the product separation and recycling process. Several first and
second generation catalysts were then evaluated under these
optimised experimental conditions (Table 3, entries 11–15). First
generation catalysts E and G failed to provide any conversion
(Table 3, entries 12, 14), and second generation indenylidene
complexes F and H afforded very low conversions (Table 3,
entries 13, 15), as also seen with second generation Grubbs
catalyst C (Table 1, entry 5). In fact, only catalyst D featuring
a Hoveyda type architecture furnished a reasonable conversion
but still below that reached with A (Table 3, entry 11). These
results demonstrate that any bulky alkylphosphine releasing
catalyst does not allow significant acrylonitrile cross-metathesis.
Having previously observed the inhibiting effect of a large
excess of acrylonitrile, the simultaneous slow addition of catalyst
and acrylonitrile was performed as a second manifold for TON
improvement, in particular when low catalyst loading was
employed. For that purpose, a reaction mixture consisting of
1 and 1 equiv. of acrylonitrile was continuously fed within
160 min with a solution of catalyst A (0.025 mol%) and the
second equivalent of acrylonitrile from two distinct syringes.
This procedure furnished 75% conversion of 1 and led to the
highest TON (3120) in formation of nitrile ester 2.
2
Cross-metathesis of methyl 10-undecenoate 1 with methyl
acrylate
With this important information and experimental data gained
from the cross-metathesis of 1 with acrylonitrile, the cross-
metathesis of 1 with methyl acrylate was also evaluated as a route
for the short chain diester 4 (Scheme 3). Such a transformation
was recently reported by Meier using solvent free conditions
employing a large excess of methyl acrylate11b or stoichiometric
2914 | Green Chem., 2011, 13, 2911–2919
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Scheme 3 Cross-metathesis of methyl 10-undecenoate 1 with methyl acrylate.
Table 4 Cross-metathesis of 1 with methyl acrylate using the single dose addition of catalysta
Entry
A (mol%)
[1] (mol L-1)
T/◦C
t (h)
Conv. (%)b
Yield (%)b
E/Zc
TON
1
2
3
4
5
0.1
0.1
0.5
0.1
0.1
0.05
0.05
0.5
0.5
0.5
100
50
50
50
r.t
3
3
3
3
3
83
84
99
94
89
82
10.8/1
13.0/1
11.1/1
12.7/1
12.2/1
830
840
200
940
890
82d
99
92d
85e
a 1 (0.5 mmol), methyl acrylate (1 mmol, 2 equiv.), toluene. b Determined by GC using dodecane as internal standard. c Determined by GC. d 2% of 3
detected. e 4% of 3 detected.
conditions.11c Solvent free conditions are preferred with regards
to green chemistry, however, they are not compatible with the
continuous slow addition of catalyst necessary to reach high
TONs and led in general to TONs below 1000.
temperature, providing 4 in 85% yield. These results are in
agreement with those reported by Meier, who showed similar
efficiency for the same reaction performed in bulk.11b However,
when the reactions were carried out under mild conditions
(50 ◦C or r.t.) trace amounts of the self-metathesis product 3
were detected. Further investigations on the reactions performed
with slow addition of catalysts provided an explanation on this
point.
As observed with acrylonitrile, the transformations performed
with slow addition of catalyst showed better performances
(Table 5). With this process it was possible to decrease the
catalyst loading down to 0.0125 mol% at 100 ◦C while main-
taining a very high 95% conversion corresponding to a TON
of 7600 and yielding 4 in 93% GC yield with only 2% of
self-metathesis product 3 obtained as a side product (Table 5,
entry 4). It is worth noting that the reaction performed almost
equally well under milder conditions (50 ◦C) furnishing 4 in
84% (GC yield) corresponding to a TON of 7200 (Table 5,
entry 5). However, the conversion dropped when the reaction
was carried out at r.t (Table 5, entry 6). The reaction profiles,
in particular the relative ratios of the desired product 4 and
side product 3, were monitored under various experimental
conditions (Fig. 4). This study revealed that the proportion of
The reaction was initially performed with 0.1 mol% of
Hoveyda catalyst A in toluene at 100 ◦C furnishing 4 in
82% GC yield (Table 4, entry 1). During this reaction, low
amounts of methyl oleate self-metathesis product were detected
by gas chromatography. As with acrylonitrile, the influence of
concentration and temperature was evaluated and it turned
out that the cross-metathesis of 1 with methyl acrylate led to
different results. In particular, the cross-metathesis involving
methyl acrylate could be performed under milder conditions and
was improved with a higher concentration of 1 (Table 4, entries
2, 4). In addition, with methyl acrylate, the stereoselectivity was
always in favor of the E isomer, the E/Z ratio being located in
the 10–13 range. Thus, the highest conversion was obtained at
50 ◦C using 0.5 mol% of catalyst and a methyl 10-undecenoate
concentration of 0.5 M (TON 200) (Table 4, entry 3). Decreasing
the catalyst loading to 0.1 mol% still provided 4 with a high
conversion and yield at 50 ◦C with a 0.5 M concentration of
1 thus leading to a TON of 940 (Table 4, entry 4). Of note,
the reaction proceeded with almost the same efficiency at room
Table 5 Cross-metathesis of 1 with methyl acrylate using slow addition of catalysta
Entry
A (mol%)
[1] (mol L-1)
T/◦C
Conv. (%)b
Yield 4 (%)b
E/Zc
TON
1
2
3
4
5
6
0.05
0.05
0.05
0.5
0.5
0.5
100
100
100
100
50
98
96
97
95
90
43
98
95
12.7/1
9.3/1
8.8/1
10.0/1
9.8/1
13.0/1
1960
3840
3880
7600
7200
3440
0.025
0.025
0.0125
0.0125
0.0125
96
93d
84e
37e
0.5
r.t
a 1 (0.5 mmol), methyl acrylate (1 mmol, 2 equiv.), toluene. Catalyst A in 2 ml of toluene was continuously added into the reaction mixture using a
syringe pump. Addition time = 2 h 40 min + 2 h 20 extra time. Total reaction time = 5 h. b Determined by GC using dodecane as internal standard.
c Determined by GC. d 2% of 3 detected by gas chromatography as the relative ratio of 1/3/4. e 6% of 3 detected by gas chromatography as the relative
ratio of 1/3/4.
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Fig. 4 Cross-metathesis of 1 (0.5 mmol) with methyl acrylate (1 mmol, 2 equiv.), toluene. Ratio measured by gas chromatography. (a) Table 5, entry
1: Catalytst A 0.05 mol%, 100 ◦C, 0.05 M. TON: 1960; (b) Table 5, entry 4: Catalytst A 0.0125 mol%, 100 ◦C, 0.5 M. TON: 7600. (c) Table 5, entry
5: Catalytst A 0.0125 mol%, 50 ◦C, 0.5 M. TON: 7200. (d) Table 5, entry 6: Catalytst A 0.0125 mol%, r.t, 0.5 M. TON: 3440.
Scheme 4 Cross-metathesis of diester 5 with acrylonitrile, methyl acrylate.
the not desired self-metathesis product 3 could reach up to 22%
(Fig. 4b) in the course of the reaction before decreasing, due to
cross-metathesis with methyl acrylate. The analysis performed
at 100 ◦C using 0.05 mol% (Fig. 4a) and 0.0125 mol% (Fig. 4b)
of catalyst A showed that at this temperature, once formed, the
self-metathesis product 3 is almost fully transformed into 4 by
cross-metathesis with methyl acrylate. The same analysis carried
out at 50 ◦C and room temperature (Fig. 4c and 4d) revealed
the formation of 3 to a lesser extent, however, due to the more
difficult transformation by cross-metathesis of internal olefins
at low temperature, once formed, 3 was not fully converted into
4 by cross-metathesis with methyl acrylate. Higher temperatures
are hence required to ensure both high conversions with low
amounts of self-metathesis product remaining at the end of the
transformation.
3. Cross-metathesis of dimethyl octadec-9-en-1,18-dioate 5
with acrylonitrile and methyl acrylate
The diester 5 is another important renewable material prepared
via biotransformation of oleic acid33 or by self-metathesis
of methyl oleate.18 Additionally, this compound provides an
access to monomers containing 11 carbon atoms (Scheme
4) whereas the previous monoester 1 furnished fatty chains
containing 12 carbon atoms. Thus, cross-metathesis of 5 with
acrylonitrile would constitute the first catalytic step leading to
C11 polyamides.
The cross-metathesis of 5 with acrylonitrile (4 equiv.) was
attempted with various catalysts (A–D) andthe Hoveydacatalyst
A showed the best performance affording 6 in 95% yield
(Table 6, entry 1). Decreasing the catalyst loading down to
Table 6 Cross-metathesis of 5 with acrylonitrilea
Entry
Cat (mol%)
t (h)
T/◦C
Conv. (%)b
5/6/8c
Yield of 6 (%)
Z/Ec
TON
1
2
3
4
5
6
7
8
A (5)
16
16
16
16
3
80
80
80
99
65
14
82
98
88
60
98
0/98/2
38/42/17
88/8/4
17/68/15
2/91/7
13/71/16
44/38/18
3/90/7
95d
2.6/1
1.0/1
3.6/1
3.1/1
2.9/1
3.2/1
3.0/1
2.8/1
n.d.
n.d.
n.d.
n.d.
98
176
600
1960
B (5)
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
88d
C (5)
D (5)
80
A (1)
100
100
100
100
A (0.5)
A (0.1)
A (0.05)
8
18
4 + 1e
a 5 (0.5 mmol), acrylonitrile (2 mmol, 4 equiv.), toluene (10 ml). b Determined by GC using tetradecane as internal standard. c Determined by GC.
d Isolated yield. e Dropwise addition of catalyst in 2 ml of toluene added over 4 h + 1 h reaction time.
2916 | Green Chem., 2011, 13, 2911–2919
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Table 7 Cross-metathesis of 5 with methyl acrylatea
Entry
A (mol%)
[5] (mol l-1)
t (h)
Conv. (%)b
Yield (%)c
E/Zd
TON
1
2
3
4
0.5
0.05
0.05
0.1
2
99
92
97
40
95 (93)
87
(90)
30
12.8/1
9.3/1
n.d.
198
3680
3880
1600
0.025
0.025
0.025
4 + 2e
4 + 2e
4 + 2e
0.5
9.3/1
a 5 (0.5 mmol), methyl acrylate (2 mmol, 4 equiv.), toluene, 100 ◦C. b Determined by GC using tetradecane as internal standard. c GC yield (isolated
yield). d Determined by GC. e Dropwise addition of catalyst in 2 ml of toluene added over 4 h + 2 h reaction time.
0.1 mol% resulted in an important drop of conversion and
increased amounts of unreacted olefin 8 (Table 6, entries 5–7). As
demonstrated for the cross-metathesis transformations of 1, the
reaction efficiency and productivity could be greatly improved
using the dropwise slow addition of catalyst. 98% conversion was
reachedwith this process with only0.05mol%ofcatalyst (TON =
1960) affording 6 in 88% yield (Table 6, entry 8). It is noteworthy
that even though this reaction involves an internal alkene the 11
carbon containing nitrile-ester 6 was produced with the same
efficiency as the 12 carbon-containing nitrile ester 2 obtained
from a terminal alkene, showing that under our conditions the
cross-metathesis of acrylonitrile with an internal olefin is not
more difficult than with a terminal one (compare Table 6, entry
8 with Table 3, entry 7).
The cross-metathesis of 5 with methyl acrylate was also inves-
tigated as a route for the production of the fatty diester 7, which
can be further derivatized to the corresponding diacid or diol.
As observed with the monoester 1, this transformation showed
better performances than the cross-metathesis with acrylonitrile
(Table 7). Single-dose addition of catalyst could be performed
at 100 ◦C with 0.5 mol% of catalyst A. In 2 h, a conversion
of 99% was reached and 7 was obtained in 93% isolated yield
(Table 7, entry 1). When the slow addition of the catalyst
was used, a TON of 3680 was obtained using 0.025 mol% of
catalyst (Table 7, entry 2). Notably, to the contrary of the cross-
metathesis of 1 with methyl acrylate, a higher concentration did
not, to a large extent, improve the reaction efficiency and was
even found detrimental when a 0.5 M concentration of 5 was
used (Table 7, entry 3, 4). Finally, the cross-metathesis reaction
between the diester 5 and methyl acrylate was attempted at
50 ◦C and room temperature but no noticeable conversions were
observed after 5 h in both cases. These latter results are in full
agreement with those obtained for the cross-metathesis of 1 with
methyl acrylate at low temperature, where it was shown that the
undesired self-metathesis product 3 did not react with methyl
acrylate at low temperature to furnish the desired diester 4
(see Fig. 4c, 4d).
4
Cross-metathesis of methyl ricinoleate 9 with acrylonitrile
and methyl acrylate
Ricinoleic derivatives are very useful renewable raw materials
that differ from the more classical oleic derivatives as they feature
an additional hydroxy functionality that confers an extra-value
to this compound and opens a new opportunity for further
derivatization reactions.28 However, the homoallylic hydroxy
group may interact with the catalyst and prevent the desired
transformation. The cross-metathesis of methyl ricinoleate with
acrylonitrile was studied using both the single dose addition
and the dropwise slow addition of catalyst (Scheme 5). This
transformation has the potential to furnish the same monomer
precursor 6 as the cross-metathesis of the diester 5 with
acrylonitrile, and an original compound 10, a precursor of a
secondary fatty amino-alcohol.
Single dose addition of 1 mol% of Hoveyda catalyst A at
80 ◦C allowed full conversion of 9 in 7 h providing 6 in 82%
isolated yield and 10 in 76% isolated yield (Table 8, entry 1).
The productivity of the reaction using catalyst A was further
improved by using the dropwise slow addition of catalyst. The
highest TON (920) was reached using 0.1 mol% of catalyst
providing 6 and 10 in 73% and 66% GC yield, respectively
(Table 8, entry 2). These first results demonstrate that the
transformation of methyl ricinoleate is more difficult to perform
than the transformation of the diester 5 also containing an
internal double bond. This result likely finds its explanation in
the presence of the hydroxyl group that could prevent an efficient
Scheme 5 Cross-metathesis of methyl ricinoleate 9 with acrylonitrile.
Table 8 Cross-metathesis of methyl ricinoleate 9 with acrylonitrilea
Entry
A (mol%)
[9] (mol L-1)
t (h)
Conv. (%)b
Yield 6/10(%)c
Z/Ed 6;10
TON
1
2
1
0.1
0.05
0.05
7
100
92
88 (82e)/83 (76e)
73/66
3.7/1;3.4/1
4.1/1;3.2/1
198
920
4 + 3f
a 9 (0.5 mmol), acrylonitrile (2 mmol, 4 equiv.), toluene, 100 ◦C. b Determined by GC using tetradecane as internal standard. c GC yield. d Determined
by GC e Isolated yield. f Catalyst in 2 ml of toluene added over 4 h + 3 h reaction time.
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Scheme 6 Cross-metathesis of methyl ricinoleate 9 with methyl acrylate.
Table 9 CM of methyl ricinoleate 9 with methyl acrylatea
Entry
A (mol%)
[9] (mol l-1)
t (h)
Conv. (%)b
Yield 7/11 (%)c
E/Z 7;11c
TON
1
2
0.5
0.1
0.5
0.05
8
100
90
89d/85d
45/78
7.2/1; 23.5/1
8.9/1; 12.2/1
200
900
4 + 2e
a 9 (0.5 mmol), methyl acrylate (2 mmol, 4 equiv.), toluene, 100 ◦C. b Determined by GC using tetradecane as internal standard. c Determined by GC.
d Isolated yield. e Catalyst in 2 ml of toluene added over 4 h + 2 h reaction time.
transformation either by coordination to the ruthenium atom or
by catalyst decomposition.34
The cross-metathesis of 9 with methyl acrylate was investi-
gated as an alternative route for the production of the fatty
diesters 7 with concomitant formation of 11 which is a potential
precursor of the corresponding fatty diol (Scheme 6).
The single dose addition of 0.5 mol% of catalyst A for the
cross-metathesis reaction of 9 with methyl acrylate at 100 ◦C
provided an almost equimolar ratio of compounds 7 and 11,
which were isolated in 89% and 85% yield, respectively (Table 9,
entry 1). The slow addition of catalyst afforded 90% conversion
using 0.1 mol% of catalyst A thus leading to the highest TON
for this reaction (900) (Table 9, entry 2). In that case, lower
yield resulted from unreacted terminal olefins obtained from the
initial cross-metathesis of 9 with methyl acrylate. Of note, the
E/Z ratios (12–24) in 11 bearing the hydroxyl substituent were
higher than the E/Z ratios of 7 isomers (7.2–8.9), suggesting
again the non-innocent influence of the hydroxyl substituent on
the transformation of 9.
to be reached. These cross-metathesis conditions have been
adapted to the cross-metathesis of the same plant oil derivatives
with methyl acrylate and it was shown that methyl acrylate
concentration was crucial for the efficient productions of a,w-
diesters with high TONs. All together, these results demonstrate
that olefin cross-metathesis applied to the transformation of
renewable fatty acid derivatives and acrylonitrile constitutes an
appropriate and realistic tool for the production of raw material
for the chemical industry, in particular for the generation of
bifunctional derivatives.
Acknowledgements
The authors are grateful to Arkema for a PhD position to XM,
to CNRS and French Ministry of research, and to the European
Network IDECAT (NOE NMP3-CT-2005-011730) for support.
The authors also wish to thank Umicore Company for fruitful
discussions.
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The Royal Society of Chemistry 2011
Green Chem., 2011, 13, 2911–2919 | 2919
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