Cross-metathesis approach to produce precursors of nylon 12 and nylon 13 from microalgae

Article abstract of DOI:10.1039/c4ra10980e

A two-step synthesis for producing methyl 12-aminododecanoate and 13-aminotridecanoate, the precursors of nylon 12 and nylon 13, from methyl oleate is described. First, methyl 11-cyano-9-undecenoate or 12-cyano-9-dodecenoate were prepared by cross metathesis of methyl oleate with either allyl cyanide or homoallyl cyanide, respectively. Subsequently, all the unsaturation of the two intermediates was hydrogenated to deliver the final products. This method represents the first synthesis of nylon 12 and 13 precursors from methyl oleate, an ester of an abundant and renewable natural fatty acid present in vegetable oil or microalgae. It also represents the shortest synthesis of nylon precursors from fatty acids, and as demonstrated in this study, can be directly applied to crude fatty acid methyl ester extracts from microalgae.

Full text of DOI:10.1039/c4ra10980e

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ARTICLE
Cross-metathesis approach to produce precursors of
nylon 12 and nylon 13 from methyl oleate
Cite this: DOI: 10.1039/x0xx00000x
Godwin Abel,†a Kim Nguyen,†b Sridhar Viamajala,a Sasidhar Varanasi,a and Kana
Yamamoto*c
Received 00th January 2012,
Accepted 00th January 2012
A
twoꢀstep synthesis for producing methyl 12ꢀaminododecanoate and 13ꢀaminotridecanoate, the
precursors of nylon 12 and nylon 13, from methyl oleate is described．First, methyl 11ꢀcyanoꢀ9ꢀ
DOI: 10.1039/x0xx00000x
undecenoate or 12ꢀcyanoꢀ9ꢀdodecenoate were prepared by cross metathesis of methyl oleate with either
allyl cyanide or homoallyl cyanide, respectively. Subsequently, all the unsaturation of the two
intermediates was hydrogenated to deliver the final products. This method represents the first synthesis of
nylon 12 and 13 precursors from methyl oleate, an ester of an abundant and renewable natural fatty acid
present in vegetable oil or microalgae. It also represents the shortest synthesis of nylon precursors from
fatty acids.
www.rsc.org/
ricinoleic acid from castor beans as the feedstock and require 4–6
steps.15ꢀ16, 20ꢀ21, 23 Synthesis of nylon 13 has not been fully studied
Introduction
except for one reported approach that involved several steps from
either erucic or lesquerolic acid, another atypical acid available from
rapeseed oil.24
Herein, we report the successful application of cross metathesis
to synthesize nylon 12 and 13 precursors from oleic acid. Our
method provides a shorter and simpler route for production of both
nylon 12 and nylon 13 from an abundant and inexpensive, and thus
preferred starting material.
Nylons are synthetic polyamides with extensive applications in
modern society. In particular, nylon 11 and 12 possess excellent
chemical properties and are widely used in automotive, medical, and
electronic industries as well as for sport equipment, back panel for
solar cells, and lenses for glasses. Nylon 13 is reported to have
similar properties to nylon 12. These nylons are produced from
amino acids or their derivatives with a corresponding number (11, 12
or 13) of carbonꢀchain backbone.1
Currently, the precursor of nylon 12 is manufactured from
petroleumꢀderived butadiene in a sixꢀstep process.2 However, there Results and discussion
is an increasing interest in use of renewable sources for production
of these amino acid precursors, because of concerns over
The previously reported cross metathesis approach to produce
environmental sustainability of petrochemical products.3 As such, the nylon 11 precursor (Figure 1, (a)) involved reacting methyl
synthetic approaches that use natural fatty acids and esters from oleate (1) or ricinoleate (2) with acrylonitrile.15, 17, 20 The resulting
plantꢀ or algaeꢀderived feedstocks are especially attractive.4ꢀ6 10ꢀcyanoꢀ9ꢀdecenoate (7) was subjected to highꢀpressure
Among the natural fatty acids, oleic acid is the predominant hydrogenation to remove all unsaturation and deliver the nylon 11
component of lipids in a large variety of vegetable oils (e.g. soy or precursor (3) (Figure 1, eq. 1). Nylon 12 precursor was also prepared
canola) as well as oleaginous microorganisms such as algae.7
in analogous fashion by cross metathesis with acrylonitrile and
The precursor of nylon 11 is manufactured from ricinoleic acid, methyl 10ꢀundecylenate (4) prepared from pyrolysis of 2 (Figure 1,
a natural fatty acid available only in castor beans.2 In this method, eq. 2). In related approaches, methyl oleate (1) or ricinoleate (2) was
the acid is first converted to its methyl ester and then subjected to first converted to their derivatives such as dimers or terminal alkenes
pyrolysis to produce 10ꢀundecyleate, which is then converted to the before subjecting to metathesis – these routes showed improved
nylon 11 precursor in two additional steps. Several other multiꢀstep throughput to the original approach, although lengthened the overall
(>4 steps) approaches to produce nylon 11 precursors from either synthetic steps.15ꢀ16, 20ꢀ21
ricinoleic acid or oleic acid derivatives are reported in patents8ꢀ14 and
journals,15ꢀ22 but have likely not been utilized for industrial process.
Since our intention was to find a direct pathway toward nylon
12 and 13 precursors from oleic acid, we attempted cross metathesis
While there is one study on a concise threeꢀstep metathesisꢀ of methyl oleate with alkenylcyanides with longer chain length
based approach for producing nylon 11 from oleic acid,17 the method (Figure 1, eq. 3). In the first step, we subjected methyl oleate to
has previously not been applied for producing nylons 12 or 13, likely cross metathesis with allyl or homoallyl cyanides with the intent of
due to challenges associated with selectivities (discussed in more generating the corresponding cyano ester intermediates 9 and 10.
detail in the Results section). The other reported methods to produce Subsequently, the double and triple bonds of these intermediates
nylons 12 and 13 from nonꢀpetrochemical sources are lengthy, and could be hydrogenated to deliver the nylon 12 and 13 precursors 5
also employ exotic fatty acids as starting materials. For example, and 6, respectively. Our approach, although related to the reported
there are several reported nylon 12 precursor syntheses that use nylon 11 synthesis,17 behaved completely differently when their
This journal is © The Royal Society of Chemistry 2013
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ARTICLE
VJieowuArrtnicalelONnlainme e
DOI: 10.1039/C4RA10980E
reaction conditions were used.25 In this report, we disclose our delivering the desired nylon precursors.
studies to overcome the issue, as well as eventual success in
(a) Cross metathesis approach by Arkema
9
CO2Me
acrylonitrile
CN
9
9
11
10
7
CO2Me
NC
CO2Me
(eq. 1)
H2N
7
10
7
10
11
7
methyl 11-aminounedecanoate (3)
(nylon 11 precursor)
X
X = H: methyl oleate (1)
X = OH: methyl ricinolate (2)
acrylonitrile
CN
9
9
CO2Me
H2N
CO2Me
9
NC
NC
CO2Me
(eq. 2)
(eq. 3)
7
11
7
10
10
12
7
10
methyl 12-aminododecanoate (5)
(nylon 12 precursor)
8
methyl 10-undecylenate (4)
(b) THIS WORK
9
CN
n
9
9
11
n
CO2Me
H2N
CO2Me
CO2Me
10
7
7
n
7
10
10
n = 1: allyl cyanide
n = 2: homoallyl cyanide
n = 1: 9
n = 1: methyl 12-aminododecanoate (5)
methyl oleate (1)
n = 2: 10
n = 2: methyl 13-aminotridecanoate (6)
(nylon 13 precursor)
Figure 1. (a) Previously reported cross metathesis approach. (b) Our approach to nylon precursors from methyl oleate.
We began our investigation of the cross metathesis step using
Subsequently, the other reaction parameters were screened to
allyl cyanide and methyl 9ꢀdecenoate (11), a model substrate for suppress dimerization and to further improve the reaction
methyl oleate (Table 1). Under the reported reaction conditions conversion. The reaction conversion was good at temperature >95
(entries 1–3), while the reaction conversion is good (>92%) at the °C; however, the best product profile was observed at 110 °C
temperature >95 °C, only 25–30% (by GC area) of the desired (entries 5 vs 7).
The conversion was further improved by a
product was seen. The complex mixture of other products comprises continuous injection of the ruthenium catalyst over 1–2 h period
unsaturated cyano esters with various alkyl chain lengths, with (entries 5 vs 8). The reactant concentration ~0.033 M was found to
molecular weight varying by 14, which led us to speculate that they provide the best selectivity for the desired reaction (entries 11, 13
arose from olefin isomerization. Other major sideꢀproducts of the and 14). The preferred molar ratio of allyl cyanide was found to be
reaction were series of dimers with structures yet to be determined.
five equivalents (entries 2 vs 3, 10 vs 12). Use of cross metathesis
In order to suppress the undesired isomerization, the reaction for oleochemical production from fatty acids has been a subject of
22, 27
was examined with several additives.22, 26 We found that addition of several reviews.19,
Consistent with other reports, Hoveydaꢀ
1,4ꢀbenzoquinone nearly completely suppressed the side reaction in Grubbs second generation catalyst showed better conversion than
our system (Table 1, entries 4). In order to fully suppress the Grubbs catalyst (entries 5 and 9) for our system. At least 2 mol% of
isomerization, 50 mol% of the additive was required (entries 12 vs this catalyst was required to achieve full conversion under the
14).
reaction conditions shown (entries 4 vs 5).
Table 1 : Crossꢀmetathesis of Methyl 9ꢀdecenoate with allyl cyanide[a]
9
9
CO2Me
CO2Me
+
NC
CN
allyl cyanide
7
7
10
10
9
methyl 9-decenoate (11)
Additive[h]
(mol%)
GC area%
Catalyst
(mol%)
Temperature
(°C)
Time
(h)
Entry
Conversion (%)
dimers
9
1
/
/
1
1
80
95
17
21
6.9
94.7
6.1
25.5
0
35.8
2[b]
3
/
1
1
2
2
2
2
2
2
2
2
2
2
95
8
5
4
6
6
6
6
4
6
6
4
4
92.2*
78.7*
92.2
48.1
84.4
42.7
49.1
93.8
64.6
37.7
84.7
78.8
28.2
52.0
49.2
20.7
56.4
23.5
27.8
44.2
39.2
16.9
42.2
58.3
21.7
7.8
4
BQ (10)
BQ (10)
AA (10)
BQ (10)
BQ (10)
BQ (10)
BQ (10)
BQ (10)
BQ (10)
BQ (50)
BQ (50)
95
5
95
17.0
4.5
6
95
7
110
95
9.0
8[c]
9[g]
10[b]
11[d]
12[e]
13[f]
14
7.8
95
3.3
110
95
11.1
11.0
4.0
110
110
110
3.0
5.5
2 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C4RA10980E
[a] Reaction conditions: To a flask containing methyl 9ꢀdecenoate (0.1 mmol), allyl cyanide (0.5 mmol), and toluene (2 mL) was added
HoveydaꢀGrubbs 2nd generation catalyst (1–2 mol%) in toluene (1 mL) dropwise over 1h. [b] 2 equiv. of allyl cyanide was used. [c] The
catalyst added in one portion. [d] 0.5mL of solvent was used for catalyst delivery; no other solvent was used. [e] 10 equiv. of allyl cyanide
was used. [f] 12 mL (11mL + 1mL) of solvent for the whole reaction was used instead of 3 mL (2 mL + 1 mL). [g] Grubbs 2nd generation
catalyst was used. [h] BB: Benzoquinone; AA: Acetic acid. * Approximate values.
poisoning (entry 5). Increasing the catalyst loading up to 4.5
It is known that solvent selection significantly influences
conversion and selectivity in metathesis reactions. In particular,
halogenated solvents are considered to be superior.28 In our
system, solvents with lower boiling point were not suitable
(Table 2, entry 2) and fluorinated solvents increased the dimer
formation (entries 3 and 5). However, use of chlorobenzene
provided good reaction conversion and better selectivity than
other solvents (entries 4 and 6).
mol% only provided similar reaction profiles (entry 6–7). To
date, we concluded that the current best reaction conditions for
this conversion to be the one used in entry 3 or 4. This
procedure reliably provides the desired 8 in ~55% yield while
suppressing olefin isomerization and dimer formation (<10 %).
Table 3: Crossꢀmetathesis of methyl oleate with allyl cyanide[a]
9
9
CO2Me
CN
9
CO2Me
10
CO2Me
7
NC
7
allyl cyanide
10
7
Table 2 : Solvent screening on cross metathesis of 9ꢀdecenoate
+
10
with allyl cyanide[a]
methyl 9-decenoate (11)
9
methyl oleate (1)
9
9
CO2Me
CO2Me
+
NC
CN
allyl cyanide
7
7
10
10
GC area%
Time Time Conv.
(h)
9
methyl 9-decenoate (11)
Entry
(h)[b] (%)
dimers
9
11
GC area%
Time
(h)
Conv.
(%)
Entry Solvent
1
2[c]
3
3
4
1
1
2
78.5
70.2
85.3
46.5
34.4
49.0
3.9
4.0
5.6
14.5
14.9
9.3
dimers
9
1
2[b]
C6H5CH3
(CH2Cl)2
C6F5Cl
4
8
2
2
5
3
78.8
41.2
95.3
90.3
77.2
93.5
58.3
17.8
60.1
62.6
18.6
5.5
3
11.6
20.6
13.8
46.0
4.1
4
4
4
3
3
2
2
87.0
38.5
86.3
55.3 (55)[h] 7.5
16.0 0.0
37.5 (56)[g] 7.1
47.1 4.1
9.2
9.8
7.0
5[d]
6[e]
3
4
C6H5Cl
C6F5CF3
C6H5Cl
7[f]
4
2
96.3
11.7
5
6[c]
71.2 (58)[d]
[a] Reaction conditions: To the flask containing methyl oleate (0.1
mmol), allyl cyanide (0.5 mmol), 1,4ꢀbenzoquinone (0.05 mmol), in
chlorobenzene (2 mL) was added HoveydaꢀGrubbs 2nd generation catalyst
(2 mol%) in chlorobenzene (1 mL) added dropwise at 110 °C. [b]
Catalyst addition time. [c] Reaction temperature: 95 °C. [d] 10 equiv. of
allyl cyanide was used. [e] 4.5 mol% of catalyst was used. [f] 3 mol% of
catalyst was used. [g] GC yield (quantified). [h] Isolated yield.
[a] Reaction condition: To the flask containing methyl oleate (0.1 mmol),
allyl cyanide (0.5 mmol), 1,4ꢀbenzoquinone (0.05 mmol), in
chlorobenzene (2 mL) was added HoveydaꢀGrubbs 2nd generation
catalyst (2 mol%) in chlorobenzene (1 mL) was added drop wise at 110
°C. [b] Reaction temperature: 80 °C. [c] 4.5 mol% of the catalyst was
used. [d] Isolated yield.
Crossꢀcoupling with homoallyl cyanide was also
investigated using both 9ꢀdecenoic acid (Table 4) and methyl
oleate (Table 5). Some reaction tuning was required in order to
achieve a good conversion with this coupling partner. In
particular, we found that the reaction conversion was sensitive to
equivalency of homoallyl cyanide. Under the optimal conditions
used for allyl cyanide metathesis, the reaction conversion was as
low as 4–5 % (Table 4, entries 5–6) or 23% if using methyl
oleate (1) (Table 5, entry 6). We suspected that this behaviour
may relate to the faster dimerization of homoallyl cyanide. In any
event, lowering the homoallyl cyanide equivalency to 1–2 equiv.
resulted in good reaction conversion and selectivity with both
substrates (Table 4, entry 2; table 5, entry 4). Thus, both methyl
9ꢀdecenoate (11) and methyl oleate (1) effectively underwent
crossꢀmetathesis reaction with nonꢀconjugated nitriles. We were
able to obtain the desired product at a comparable isolated yield
of 43% from this reaction.
Subsequently, these optimized cross metathesis conditions
for methyl 9ꢀdecenoate (11) were applied to methyl oleate (1)
(Table 3). It was observed that dimerization was suppressed
with this substrate likely due to its lower reactivity. Use of 1
instead of 11 made the product analysis more complex, because
of formation of nonꢀvolatile byꢀproducts, including methyl 9ꢀ
decenoate (11).
We have examined several reaction parameters in the
attempt to optimize the reaction. We first examined use of
lower temperature (95 °C) with hope to lower the catalyst
deactivation and increase the selectivity. However, the lower
temperature reactions resulted in increased formation of 11 and
dimers (entry 2). To suppress the catalyst decomposition, the
catalyst addition time was further extended. This attempt was
partially successful and extending the time to 3h improved the
conversion as well as the selectivity for 9 (entries 3–4).
Attempt to drive 11 to desired 9 with use of excess of cyanide
led to low reaction conversion, possibly due to catalyst
Table 4: Crossꢀmetathesis of 9ꢀdecenoate with homoallyl cyanide
9
9
CO2Me
NC
CO2Me
+
7
CN
10
7
10
methyl 9-decenoate (11)
homoallyl cyanide
10
Entry Time
cyanide Conv.
GC area %
This journal is © The Royal Society of Chemistry 2012
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VJieowuArrtnicalelONnlainme e
ARTICLE
(h)
DOI: 10.1039/C4RA10980E
strong hydride reducing agents such as lithium aluminium
hydride or borane, or hydrosilylation with Lewis acids such as
(mmol)
(%)
dimers
10
1
2
3
4
6
6
4
6
0.1
82.2
83.5
78.0
78.9
43.8
51.2
48.1
48.9
31.8
27.6
25.0
24.1
titanium isopropoxide.
Alternately, strong heterogeneous
0.15
0.15
0.25
catalysts such as Raney nickel or cobalt can be used to catalyze
addition of molecular hydrogen, but reaction conditions are harsh
and only moderate selectivity is afforded.
Studies on
hydrogenation of nitriles with homogenous catalysts have been
limited although catalysts based on rhodium, iridium, rhenium,
and ruthenium have recently been investigated.29 Most recent
studies used ruthenium complexes, which by far gave the best
5
6
7
6
4
6
0.25
0.5
0.5
56.3
4.7
4.2
38.5
4.0
4.2
15.9
0.0
0.6
[a] Reaction condition: 0.1 mmol of methyl oleate, 50 mol% 1,4ꢀ
Benzoquinone,
mol% of HoveydaꢀGrubbs 2nd generation in
chlorobenzene (1 mL) added dropwise into 1.5mL of chlorobenzene at 110
oC.
selectivity under mild reaction conditions.
Many studied
2
catalytic systems use phosphine ligands as well as potassium tertꢀ
butoxide additive. Typical reactions conditions are 80–140 ºC at
H2 pressure of 14–75 bars. It was also shown that milder reaction
conditions could be used when the phosphine ligands of the metal
complex are replaced with carbene ligands.
Finally, the
Table 5: Crossꢀmetathesis of methyl oleate with homoallyl
cyanide[a]
metathesis catalyst has also been shown to facilitate the
hydrogenation reaction, and that it is possible to use residual
catalyst from metathesis for hydrogenation.20ꢀ21
9
9
9
CO2Me
CO2Me
10
CO2Me
CN
7
7
7
homoallyl cyanide
+
10
10
CN
The previous studies for hydrogenation of fatty acid
derivatives indicated that either the Grubbs or HoveydaꢀGrubbs
second generation catalyst would be effective.20ꢀ21 However, only
Grubbs second generation catalyst provided the desired product
in our experiments. Using this catalyst, we found that toluene,
benzene, or chlorobenzene solvents were all suitable and the
reaction temperature of 80 ºC provided the best overall
conversion. Thus these reaction conditions were adopted for the
subsequent studies (Table 6). The base additive is essential in
this catalyst system, and 30 mol% of potassium tertꢀbutoxide was
sufficient to ensure the full reaction conversion (entries 1–2 vs 3–
11). The catalyst loading of >2 mol% was found essential for
good conversion (entries 3–5; 8–10). The reaction mixture was
kept for 17–44 h under hydrogen pressure in between 20–25 bar.
These reaction conditions consistently provided >50% (by GC
area) of the desired methyl 12ꢀaminododecanoate (5) (entries 4,
6). The same reaction conditions, when used to hydrogenate C13
cyano ester (10), resulted in comparable yields (entry 6,7 vs
9,10). These products were readily isolated and purified by
column chromatography to yield 62% and 53% of the nylon 12
and nylon 13 precursors.
10
methyl 9-decenoate (11)
methyl oleate (1)
GC area %
Time cyanide Conv.
(h)
Entry
(mmol) (%)
Dimer
10
11
1
2
3
4
5
6
6
6
8
4
6
6
0.15
0.25
0.25
0.25
0.3
68.6
78.8
74.4
88.7
77.6
23.3
31.5
42.9
34.5
15.3
10.9
12.6
7.8
10.1
9.9
52.3 (42.9)[b] 8.7
16.2
16.8
11.7
38.0
0.4
7.5
6.6
0.5
[a] Reaction condition: 0.1 mmol of methyl oleate, 50 mol% 1,4ꢀ
Benzoquinone,
mol% of HoveydaꢀGrubbs 2nd generation in
chlorobenzene (1 mL) added dropwise into 1.5mL of chlorobenzene at
110 oC. [b] Isolated yield.
2
In the second step, although hydrogenation of olefins is an
established reaction that many catalysts are available, the
reduction of nitriles to amines conventionally uses stoichiometric
Table 6 : Hydrogenation of methyl 11ꢀcyanoundecꢀ9ꢀenoate and 12ꢀcyanododecꢀ9ꢀenoate[a]
9
9
9
n
11
n
CO2Me
H2N
CO2Me
CO2Me
+
NC
NC
7
7
7
n
10
10
10
n = 1:
9
n = 1: methyl 12-aminododecanoate (5)
n = 2: methyl 13-aminotridecanoate (6)
n = 1: 12
n = 2: 13
n = 2: 10
GC area (%)
Cat.
tꢀBuOK
Pressure
(Bar)
Time
(h)
Entry
n
(mol %) (mol %)
5 or 6
12 or 13
By products
1
2
3
4
5
6
7
1
1
1
1
1
1
1
1
3
1
2
3
3
3
15
15
30
30
30
30
30
20
25
20
20
20
25
24
20
20[b]
1.4
71.6
55.6
83.0
10.6
2.3
15.4
29.6
1.6
6.8
17
10.4
78.3
68.5
56.8
17
6.2
17
20[b]
17.4
27.0
16.2
4.1
44
68.6 (62)[c] 2.6
41.0 (53)[c] 30.3
8
9
2
2
1
2
30
30
20
20
19
19
16.9
30.0
58.2
2.9
4 | J. Name., 2012, 00, 1-3
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ARTICLE
DOI: 10.1039/C4RA10980E
10
2
3
30
20
19[d]
43.3
2.1
42.2
[a] Reaction condition: 20 mg of methyl 11ꢀcyanoꢀ9ꢀundecenoate, 30 mol% of tꢀBuOK, 3 mol% of Grubbs 2nd
generation catalyst, 3mL of chlorobenzene at 80 °C, 30 bars during 20 h with stirring. [b] Isolated yield. [c]
Extending the reaction period for additional 45 h under otherwise same conditions did not improve the product
profile.
10. J.ꢀL. Couturier and J.ꢀL. Dubois, Pat., 2011ꢀ57065 2978763 A1,
2013.
Conclusion
11. J.ꢀL. Couturier and J.ꢀL. Dubois, Pat., 2012ꢀFR51770 2013017782
A1, 2013.
We have demonstrated synthesis of nylon 12 and nylon 13
precursors from methyl oleate via cross metathesis reactions
with allyl and homoallyl cyanides, respectively. Our work
represents the shortest synthetic route to these precursors from
the abundantly available oleic acid. The key feature of our
approach includes use of 1,4ꢀbenzoquinone as additive, which
completely supressed the undesired isomerization side reaction
during the metathesis step. Our approach not only enables
preparation of nylon 12 and 13 precursors directly from methyl
oleate, but also offers new pathways to access precursors of
other nylons of different chainꢀlength, economically and
sustainably.
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Acknowledgements
This work was financially supported by National Science Foundation
(CHEꢀ1230609) and the University of Toledo (Interdisciplinary
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a Department of Chemical and Environmental Engineering, University of
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b Current address: 270 Rue du Maconnais, 73000 Chambery, France.
c Department of Chemistry and Biochemistry, University of Toledo,
2801 W. Bancroft St. Toledo, OH 43606. Eꢀmail:
4
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kana.yamamoto@utoledo.edu
†
These authors contributed equally to this study.
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J. Name., 2012, 00, 1-3 | 5

RSC Advances
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DOI: 10.1039/C4RA10980E
Green Chemistry
RSCPublishing
Cross-metathesis approach to produce precursors of
nylon 12 and nylon 13 from methyl oleate
Godwin Abel,†a Kim Nguyen,†b Sridhar Viamajala,a Sasidhar Varanasi,a and Kana
Yamamoto*c
A two-step synthesis for producing nylon
Olefin cross metathesis
9
12 and 13 precursors from methyl oleate
CN
n
9
n
CO2Me
CO2Me
10
7
NC
is described. This method represents the
first and shortest synthesis to directly
access these precursors from methyl
oleate, an ester of an abundant and
renewable natural fatty acid present in
vegetable oil or microalgae.
7
10
methyl oleate
9
11
Hydrogenation
H2N
CO2Me
(abundant fatty acid from
many vegetable oil and
oleagenous microorganisms)
7
n
10
n = 1: Nylon 12 precursor
n = 2: Nylon 13 precursor
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 1