Cross metathesis of bio-sourced fatty nitriles with acrylonitrile

Article abstract of DOI:10.1007/s00706-015-1480-1

We report the cross metathesis of two olefinic partners containing different types of nitrile functionality. Thus, cross metathesis of fatty nitriles with acrylonitrile have been achieved with olefin metathesis ruthenium catalysts. 10-Undecenenitrile provides 2-dodecenedinitrile with a high turnover number of 13,280 in the green solvent, diethyl carbonate. Cross metathesis with the internal carbon-carbon double bond of oleonitrile gave the expected products, and the cleavage of the internal double bond proved to be more difficult probably owing to faster catalyst decomposition. Graphical abstract: [Figure not available: see fulltext.]

Full text of DOI:10.1007/s00706-015-1480-1

Monatsh Chem
DOI 10.1007/s00706-015-1480-1
ORIGINAL PAPER
Cross metathesis of bio-sourced fatty nitriles with acrylonitrile
1
Johan Bidange1 Cedric Fischmeister Christian Bruneau1 Jean-Luc Dubois2 Jean-Luc Couturier3
•
•
•
•
´
Received: 25 March 2015 / Accepted: 12 April 2015
Ó Springer-Verlag Wien 2015
Abstract We report the cross metathesis of two olefinic
partners containing different types of nitrile functionality.
Thus, cross metathesis of fatty nitriles with acrylonitrile
have been achieved with olefin metathesis ruthenium cat-
alysts. 10-Undecenenitrile provides 2-dodecenedinitrile
with a high turnover number of 13,280 in the green solvent,
diethyl carbonate. Cross metathesis with the internal car-
bon–carbon double bond of oleonitrile gave the expected
products, and the cleavage of the internal double bond
proved to be more difficult probably owing to faster cata-
lyst decomposition.
Keywords Homogeneous catalysis Á
Ruthenium catalysis Á a,x-Dinitriles Á Renewables Á
Green chemistry
Introduction
In the context of sustainable chemistry, the use of renew-
able and bio-sourced carbon feedstocks has a strong
potential to complement and replace petrochemical re-
sources [1–3]. Among natural resources, fats and oils
derived from triglycerides have found a place of choice for
the access to biofuels [4, 5], polymers [6–9], and fine
chemicals [10–12]. Taking advantage of the reactivity of
carbon–carbon double bonds, olefin cross metathesis is
especially appropriate to shorten carbon chains by cleavage
of unsaturations by ethenolysis [13–18], and to introduce
functional groups at the terminal or internal position of
unsaturated fatty acid derivatives. Introduction of ester
groups to produce diesters, precursors of polyesters, has
been achieved by cross metathesis with acrylates [19–21].
Acrolein has also been used as cross metathesis partner to
introduce a reactive aldehyde that can be easily trans-
formed into a fatty alcohol or an amine derivative [22–24].
Functional allylic partners such as allylic halide [25, 26]
or acetate [27, 28] have also been used to introduce a re-
active allylic functionality at the end of a fatty carbon
chain. Another important cross metathesis partner that al-
lows further transformation into amines is acrylonitrile
[29]. It has been considered for a long time as a reluctant
substrate for cross metathesis and has been applied for fats
and oils transformations only when ruthenium catalysts
bearing a chelating benzylidene carbene ligand appeared
[30, 31]. Thus, undec-10-enoic acid and methyl ester [32],
undecyl-10-enic aldehyde [22] bearing a terminal double
Graphical abstract
Olefin metathesis from renewables
NC
( )7
CN
NC
( )8
NC ( )7
renewables
CN
CN
NC ( )7
Dedicated to Franz Stelzer for his important contribution to polymer
science.
& Christian Bruneau
christian.bruneau@univ-rennes1.fr
1
OMC-Organometallics : Materials and Catalysis, Center for
Catalysis and Green Chemistry, Institut des Sciences
´
chimiques de Rennes, UMR 6226 CNRS, Universite de
Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France
2
3
ARKEMA France, Colombes, France
ARKEMA France, Pierre-Benite, France
123

J. Bidange et al.
bond, and methyl oleate [32, 33], octadec-9-enoic diacid
and diester [32] as internal olefins reacted efficiently with
acrylonitrile in the presence of the second generation
Hoveyda catalyst giving access to a,x-bifunctional prod-
ucts. To our knowledge, cross metathesis of
10-undecenenitrile with methyl acrylate represents a scarce
example of metathesis involving an unsaturated bio-
sourced fatty nitrile with an electron deficient olefin [34].
We now show that cross metathesis of 10-undecenenitrile
and oleonitrile with acrylonitrile can be achieved with
Hoveyda type catalysts to give a,x-dinitriles, precursors of
diamine monomers for polyamide preparation, and mono-
nitriles that can be hydrogenated into fatty amines.
reaction [37] and only a low reactivity producing but-2-
enedinitrile at high catalyst loading (2–10 mol%) was
reported with a third generation ruthenium(NHC)(ben-
zylidene)(bis-(pyridine)) catalyst (NHC = bis-(2,6-xylyl)-
imidazolidinylidene) [38]. As always observed with acry-
lonitrile as cross metathesis partner, the (Z)-dinitrile 3 was
obtained as the major stereoisomer in variable ratios (from
4.2 to 7.2), and the efficiency of the reaction was improved
in diluted conditions (Table 1, entries 2 and 3). The
negative effect of high concentration of nitrile substrates
has already been pointed out with ruthenium catalysts and
also very early with rhenium catalysts [39], and was at-
tributed to catalyst poisoning by the nitrile functionality.
Increasing the reaction temperature from 80 to 120 °C al-
lowed achieving higher conversions from 88 to 97 %
(entries 3–5).
Results and discussion
Other ruthenium catalysts were then tested with the
objective of reaching high turnover numbers (TON)
(Scheme 2). Hoveyda type catalysts, which have shown
their efficiency in cross metathesis with acrylonitrile, and
ruthenium indenylidene complexes that are known for their
robustness and efficiency in cross metathesis were selected.
The best conditions obtained with I in the initial screening,
e.g. 0.5 mol% of catalyst in toluene at 120 °C for 5 h with
a substrate 2 concentration of 0.05 M, were applied. As
depicted in Table 2, the first generation ruthenium in-
denylidene catalyst VI was not reactive and the
corresponding second generation catalyst VII exhibited
poor reactivity. Complex VIII showed interesting catalytic
activity (entry 7) but the best catalysts were obviously in
the series of chelating benzylidene ruthenium complexes
(entries 1–4) leading to TONs of about 180–190. We have
already shown that organic dialkyl carbonates were green
solvents of choice for olefin metathesis, and again it ap-
peared that the use of diethyl carbonate (DEC) as solvent
with high boiling point (126–128 °C) led to very similar
results (entries 1 and 8). Under these conditions of high
catalyst loading, it was difficult to select a more active
catalyst among I, II, III, and IV.
Cross metathesis of 10-undecenenitrile
with acrylonitrile
10-Undecenenitrile is a bio-sourced product arising from
castor oil. Thermal cleavage of methyl ricinoleate produces
methyl 10-undecenoate [35]. Hydrolysis into the corre-
sponding acid followed by ammoniation/dehydration
provides 10-undecenenitrile [36].
The cross metathesis of the terminal olefin 10-undece-
nenitrile (2) with acrylonitrile (1) was first investigated
(Scheme 1). This reaction produced the unsaturated 2-do-
decenedinitrile (3) together with ethylene.
Based on our knowledge on cross metathesis of fatty
acid derivatives with acrylonitrile, the second generation
Hoveyda catalyst I was selected to investigate the possi-
bility of achieving this transformation (Table 1). In toluene
as solvent, using 0.5–1 mol% of catalyst and 2 equivalents
of acrylonitrile, the cross metathesis reaction took place
efficiently in short reaction time when the temperature was
higher than 80 °C. The reaction was selective as the ex-
pected stereoisomers of 3 were formed as major products
with only trace amounts of undesired products, which were
probably resulting from cross metathesis of acrylonitrile
with 9-undecenenitrile resulting from double bond migra-
tion. In particular, no C20 unsaturated dinitrile (9-
eicosenedinitrile) resulting from self-metathesis of 2 was
detected, and self-metathesis of acrylonitrile is not ex-
pected to occur as it has been shown to be a difficult
In previous works on cross metathesis of acrylonitrile
with fatty acid esters, we have shown a very positive effect
on the TONs of the slow addition of the catalyst. This
effect was attributed to short lifetime of the catalyst due to
fast decomposition at high catalyst concentration. There-
fore, the slow addition of a catalyst solution to the reaction
mixture was explored by syringe-pump addition over a
period of 2.7 h followed by 2.3 h reaction time (Table 3).
To significantly increase the TONs of the reaction, cata-
lysts I, II, III, IV, and VIII were chosen to perform the
cross metathesis of 1 and 2 under these conditions with
decreasing catalyst loadings at 100 and 120 °C. First, only
the catalyst was added dropwise with a syringe pump
(entries 1–5), and then the catalyst and 1 equivalent excess
Scheme 1
Ruthenium catalyst
H2C CH2
NC
NC
CN
( )8
( )8
+
CN
2
1
3
123

Cross metathesis of bio-sourced fatty nitriles…
Table 1 Cross metathesis of 10-undecenenitrile and acrylonitrile with catalyst I
Entry
Catalyst loading/mol%
[2]/mol dm-3
Temp./°C
Reaction time/h
Conv./%
Yield of 3/% (Z/E ratio)
1
2
3
4
5
1
0.1
80
80
3
3
3
4
5
78
66
88
89
97
75 (4.8)
65 (7.2)
87 (4.2)
88 (5.1)
96 (5.5)
0.5
0.5
0.5
0.5
0.1
0.05
0.05
0.05
80
100
120
Reaction conditions: 10-undecenenitrile (0.5 mmol), acrylonitrile (1 mmol), 5 cm3 or 10 cm3 toluene, catalyst I (0.005 or 0.0025 mmol),
conversion of 2 and yield of 3 determined by GC using dodecane as internal standard
Scheme 2
Mes
Cl
Mes
Cl
Mes
Cl
N
N
N
N
N
N
Mes
Mes
O
Mes
Ru
O
Ru
O
Ru
O
Cl
Cl
Cl
O
S
NMe2
O
I
III
II
DIPP
Mes
Cl
N
N
N
N
Cy3P
Ph
Cl
Cl
DIPP
Mes
O
Ru
Ru
O
Ru
O
Cl
Cl
Cl
PCy3
O
CF3
N
H
V
IV
VI
N
Cl
N
Mes
N
N
Mes
Mes
Mes
Ph
Ph
Cl
Mes: mesityl (2,4,6-trimethylphenyl)
DIPP: 2,6-diisopropylphenyl
Ru
Ru
Cl
Cl
PCy3
N
VII
VIII
of acrylonitrile were added simultaneously via two sy-
ringes pumps to decrease the duration of their detrimental
interaction at high temperature in the reaction mixture.
With this technique, at 100 °C in toluene, the conver-
sions were satisfactory and TONs could be increased to
6000 with catalysts II and III (entries 7, 8). However, it
became apparent that when the catalyst loading decreased,
the activities of catalysts I, IV, and VIII were lower than
those of II and III. The decrease of conversion induced by
lower catalyst loading could be compensated by increasing
the reaction temperature. Owing to its higher boiling point,
diethyl carbonate was preferable to toluene for using the
slow addition of catalyst procedure. The higher catalytic
efficiency of II was confirmed under low catalyst loading
(0.00625 mol%) and a TON of 12,800 was reached (entry
17). Catalyst V featuring a DIPP-NHC ligand and an iso-
propoxybenzylidene ligand was also very efficient (entry
20). It can be noted that the most efficient catalysts II and
V are equipped with isopropoxybenzylidene ligands, which
are known to favour fast initiation of the metathesis pro-
cess. The smaller differences between conversions and
isolated yields observed in DEC (entries 11–20) as com-
pared to toluene (entries 1-19) showed that the reaction was
cleaner in diethyl carbonate. In addition, the beneficial
impact of this solvent is also illustrated by the much lower
conversion observed in p-xylene at 0.00625 mol% catalyst
loading with catalyst I, which gave only 59% conversion of
2 (entries 16 and 21).
123

J. Bidange et al.
Cross metathesis of oleonitrile with acrylonitrile
Table 2 Cross metathesis of 10-undecenenitrile and acrylonitrile:
screening of ruthenium catalysts
Oleonitrile (4) is a fatty nitrile that is prepared by ammo-
niation/dehydration of oleic acid. Ethenolysis of oleonitrile
has been recently reported and the difficulty to reach high
turnover numbers with the crude material has been pointed
out [40]. Cross metathesis of oleonitrile with acrylonitrile
(1) can potentially produce the four main products 5–8
depending on the relative efficiencies of the primary and
secondary metathesis transformations (Scheme 3).
Entry
Catalyst
Conversion/%
Yield/%
Z/E ratio
TON
1
2
3
4
5
6
7
8a
I
97
93
91
91
0
84
82
80
81
–
3.0
2.3
2.5
2.5
–
188
186
182
182
–
II
III
IV
VI
VII
VIII
I
13
83
91
–
3.5
2.4
2.8
26
73
–
166
182
Each pure nitrile-containing product was isolated for
quantitative determinations by gas chromatography. Com-
pounds 5 and 6 were isolated by silica gel chromatography
from oleonitrile/acrylonitrile cross metathesis, and 7 from
ethenolysis of 4 [40], 1-decene (8) being a commercially
available product. To ensure maximum formation of nitrile
products, an excess of acrylonitrile was necessary.
Reaction conditions: 10-undecenenitrile (0.5 mmol), acrylonitrile
(1 mmol), 10 cm3 toluene, catalyst I (0.0025 mmol, 0.5 mol%),
120 °C, 5 h, conversion of 2 determined with dodecane as internal
standard. Isolated yields
TON conversion/catalyst loading
a
Solvent: DEC
We first explored the reaction in diluted solution of
toluene ([4] = 0.05 M) at 100 °C with high catalyst load-
Table 3 Cross metathesis of 10-undecenenitrile and acrylonitrile: slow addition of catalyst and acrylonitrile
Entry
Catalyst/mol%
Solvent
Temp./°C
Conv./%
Yield/%
Z/E ratio
TON
1780
1
I (0.05)
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
DEC
100
100
100
100
100
100
100
100
100
100
120
120
120
120
120
120
120
120
120
120
120
89
92
92
85
87
67
76
74
62
51
84
93
91
87
60
76
80
76
68
83
59
80
83
75
76
82
59
66
63
53
43
80
90
87
84
53
70
76
73
64
78
52
2.7
3.6
3.4
3.2
3.8
2.0
2.0
2.2
2.6
3.0
3.4
2.9
3.1
3.2
3.5
3.4
3.4
3.4
3.5
3.2
3.1
2
II (0.05)
1840
1840
3
III (0.05)
4
IV (0.05)
1700
5
VIII (0.05)
I (0.0125)a
II (0.0125)a
III (0.0125)a
IV (0.0125)a
VIII (0.0125)a
I (0.0125)a
II (0.0125)a
III (0.0125)a
IV (0.0125)a
VIII (0.0125)a
I (0.00625)a
II (0.00625)a
III (0.00625)a
IV (0.00625)a
V (0.00625)a
I (0.00625)a
1740
6
5360
7
6080
8
5920
9
4960
10
11
12
13
14
15
16
17
18
19
20
21
4080
6720
DEC
7440
DEC
7280
DEC
6960
DEC
4800
DEC
12,160
12,800
12,160
10,880
13,280
8320
DEC
DEC
DEC
DEC
p-Xylene
Reaction conditions: 10-undecenenitrile (0.5 mmol), acrylonitrile (1 mmol), 8 cm3 solvent, conversion of 2 determined with dodecane as internal
standard. Isolated yields
Injection of a catalyst solution (2 cm3 added within 2.7 h) then 2.3 h prolonged heating
TON conversion/catalyst loading
a
Initial introduction of 1 equiv. of acrylonitrile (0.5 mmol) and injection of the catalyst ? 1 equiv. of acrylonitrile (2 cm3 added within 2.7 h)
then 2.3 h prolonged heating
123

Cross metathesis of bio-sourced fatty nitriles…
Scheme 3
Conclusion
NC ( )7
( )7
NC ( )7
CN
( )7
8
We have shown that cross metathesis of 10-undecenenitrile
with acrylonitrile takes place efficiently with Hoveyda type
catalysts at 120 °C in diethyl carbonate as solvent with
continuous addition of the catalyst and the excess of
acrylonitrile. Under the best conditions, a high turnover
number of 13,280 at 83 % conversion was obtained with
catalyst V. Cross metathesis of acrylonitrile with oleonitrile
led to the formation of four main products together with
self-metathesis products that appeared at low catalyst
loading. Turnover numbers close to 4000 could be obtained
with high conversions, but a drop of conversion rapidly
occurred when the catalyst loading was decreased below
0.0125 mol%.
4
Ruthenium catalyst
5
+
CN
NC
NC ( )7
( )7
1
6
7
Table 4 Cross metathesis of oleonitrile and acrylonitrile
Entry Catalyst/mol% Conversion/% TON Selectivity SM/5/6/7/8
1
I (0.5)
98
98
98
97
97
98
96
96
86
92
83
94
56
196
2
II (0.5)
196
3
III (0.5)
IV (0.5)
I (0.25)
196
4
194
5
388
Experimental
6
II (0.25)
III (0.25)
IV (0.25)
I (0.025)
II (0.025)
III (0.025)
V (0.025)
V (0.0125)
392
7
384
All reactions were carried out using Schlenk tube tech-
niques. Toluene was dried using an MBraun Solvent
Purification System. 10-Undecenenitrile and oleonitrile
were supplied by Arkema, distilled under vacuum and
stored under argon. Acrylonitrile was purchased from
Acros Organics and stored under Argon over 4 A MS
8
384
9
3440 16/39/35/6/4
3680 16/44/34/3/3
3320 13/36/38/8/5
3760 15/41/35/5/4
4480 22/33/29/7/9
10
11
12
13
1
followed by distillation over P2O5 prior to use. H NMR
spectra were recorded at 300 MHz and 13C NMR spectra
were recorded at 75.5 MHz on a Bruker 300 WB spec-
trometer. Reactions were monitored using a Shimadzu
2014 gas chromatograph equipped with Equity TM-1
Fused Silica capillary column. Pure products were obtained
by column chromatography on silica gel (Merck Silica Gel
60) using mixtures of petroleum ether and diethyl ether as
the eluent.
Reaction conditions: oleonitrile (0.5 mmol), acrylonitrile (2 mmol),
8 cm3 toluene, conversion of 4 and selectivity were determined by
GC using dodecane as internal standard. Injection of a catalyst so-
lution (2 cm3 added within 1 h) then 3 h prolonged heating
TON conversion/catalyst loading, SM self-metathesis product
ing (0.5 mol%) and 4 equivalents of acrylonitrile using
directly the slow addition of catalyst technique. Catalysts I,
II, III, and IV were active and led to 98 % conversion after
4 h, which corresponds to a TON of 196 (Table 4, entries
1–4). No self-metathesis products were detected with this
high catalyst loading, but the 4 expected products were
formed in various proportions. However, probably due to
higher reactivity of terminal olefins with acrylonitrile in
secondary cross metathesis processes, the dinitrile 5 and
mononitrile 6 were the major products. Similar results were
obtained when the catalyst loading was decreased to
0.025 mol% and a TON of 3760 with 94 % conversion was
obtained with catalyst V. However, products resulting from
self-metathesis were produced when the catalyst loading
decreased. It was possible to decrease the catalyst loading
to 0.0125 mol% but the conversion dropped to 56 %,
which gave a slightly higher TON of 4480. Attempts to
decrease the catalyst loading in diethyl carbonate did not
improve the results with these substrates.
General procedure for the cross metathesis
of 10-undecenenitrile with acrylonitrile
in diethylcarbonate (slow addition of catalyst)
10-Undecenenitrile (2, 82 mg, 0.5 mmol, 1 equiv.) and
26.5 mg of acrylonitrile (1, 0.5 mmol, 1 equiv.) were dis-
solved in 8 cm3 of DEC with dodecane as internal
standard. The desired amount of catalyst and 1 equivalent
of acrylonitrile (0.5 mmol, 26.5 mg) were dissolved in
2 cm3 of DEC and added dropwise over a period of 2 h
40 min into the reaction mixture heated at 120 °C. After
completion of the addition, the reaction was stirred for 2 h
20 min. After a total reaction time of 5 h, ethyl vinyl ether
was added and a sample was collected for GC analysis.
After solvent evaporation, the product was purified by
column chromatography over silica gel using a mixture of
123

J. Bidange et al.
4.83-5.07 (m, 2H, CH=CH2), 5.70–5.84 (m, 1H, CH=CH2)
ppm; 13C NMR (75 MHz, CDCl3): d = 17.1, 25.2, 27.5,
28.1, 28.3, 28.3, 114.1, 115.3, 139.2 ppm.
petroleum ether/diethyl ether (9/1) as eluent to furnish 3 as
a mixture of E and Z isomers.
2-Dodecenedinitrile (3, C12H18N2, Z:E = 4)
1H NMR (300 MHz, CDCl3): d = 1.34–1.72 (m, 12H, 6
CH2), 2.18–2.47 (m, 4H, NCCH2 ? CH2CH=CHCN),
5.30–5.37 (m, 1H, CH=CHCN, Z ? E), 6.49 (dt, 0.8H,
3J = 10.9, 7.7 Hz, CH=CHCN, Z), 6.72 (dt, 0.2H,
3J = 16.3, 7.0 Hz, CH=CHCN, E) ppm; 13C NMR
(75 MHz, CDCl3): d = 17.1, 25.3, 27.6, 28.1, 28.6, 28.8,
28.9, 29.0, 31.8, 33.3, 99.6, 99.8, 116.1, 119.8, 155.1,
156.0 ppm; HRMS: [M?Na]? calcd 213.13677, found
213.1366.
Acknowledgments The research leading to these results has re-
ceived funding from the European Union Seventh Framework
Programme (FP7/2007–2013) under grant agreement n° 241718
EuroBioRef. The authors thank Arkema for a fruitful collaboration
and for providing 10-undecenenitrile and oleonitrile. The authors also
thank Umicore Precious Metals Chemistry, Hanau, Germany, for a
loan of ruthenium catalysts.
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1H NMR (300 MHz, CDCl3): d = 1.34–1.73 (m, 10H, 5
CH2), 2.18–2.45 (m, 4H, NCCH2 ? CH2CH=CHCN), 5.31
(d, 1H, 3J = 11.0 Hz, CH=CHCN, Z ? E), 6.47 (m,
0.76H, CH=CHCN, Z), 6.70 (m, 0.24H, CH=CHCN, E)
ppm; 13C NMR (75 MHz, CDCl3): d = 17.1, 25.2, 27.4,
28.0, 28.4, 28.6, 31.7, 33.2, 99.6, 99.8, 116.0, 119.8, 155.0,
155.9 ppm; HRMS: [M?Na]? calcd 199.12112, found
199.1210.
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2-Undecenenitrile (6) [41]
1H NMR (300 MHz, CDCl3): d = 0.89 (t, 3H, CH3), 1.29-
1.50 (m, 12H, 6 CH2), 2.19–2.27 (m, 0.64H, CH2-
CH=CHCN, E), 2.40–2.47 (m, 1.36H, CH2CH=CHCN,
Z), 5.30–5.36 (m, 1H, CH=CHCN, Z ? E), 6.50 (dt, 0.68H,
3J = 10.8, 7.8 Hz, CH=CHCN, Z), 6.73 (dt, 0.32H,
3J = 16.3, 7.0 Hz, CH=CHCN, E) ppm; 13C NMR
(75 MHz, CDCl3): d = 14.1, 22.6, 27.6, 28.2, 29.0, 29.1,
29.2, 31.8, 31.9, 33.3, 99.4, 99.6, 116.1, 155.3, 156.2 ppm.
9-Decenenitrile (7) [40, 42]
1H NMR (300 MHz, CDCl3): d = 1.29–1.65 (m, 10H, 5
CH2), 2.17–2.41 (m, 4H, NCCH2 ? CH2CH=CHCN),
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