Valorization of Madagascar's CNSL via the synthesis of one advanced intermediate (3-Pentadecylcyclohexanone)

Article abstract of DOI:10.1016/j.tetlet.2017.04.093

A unique advanced intermediate: 3-Pentadecylcyclohexanone was synthetized from the crude product which contained a mixture of cardanol, cardol and 2-methylcardol, which was hydrogenated onto Pd/C at 80 °C. From this alkylated cyclohexanone: C15 alkylated adipic acid, caprolactam, caprolactone, were synthetized in high yields, such products may have many potentially applications in polymer chemistry. The condensation of the 3-pentadecyl-cyclohexanone and triethylene glycol in oxidative or reductive conditions gave aryl ether and cyclohexyl ether, this may be a way to prepare intermediate for surfactant chemistry. Therefore we show that Cashew Nut Shell Liquid (CNSL) may lead to numerous useful compounds thank to the preparation of a unique advanced intermediate.

Full text of DOI:10.1016/j.tetlet.2017.04.093

Accepted Manuscript
Valorization of Madagascar’s CNSL via the synthesis of one advanced inter-
mediate (3-Pentadecylcyclohexanone)
Andrianarivo Irène Rahobinirina, Maonja Finaritra Rakotondramanga,
Alexandra Berlioz-Barbier, Estelle Métay, Voahangy Ramanandraibe, Marc
Lemaire
PII:
S0040-4039(17)30554-3
DOI:
http://dx.doi.org/10.1016/j.tetlet.2017.04.093
TETL 48885
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
31 March 2017
27 April 2017
28 April 2017
Please cite this article as: Rahobinirina, A.I., Rakotondramanga, M.F., Berlioz-Barbier, A., Métay, E.,
Ramanandraibe, V., Lemaire, M., Valorization of Madagascar’s CNSL via the synthesis of one advanced
intermediate (3-Pentadecylcyclohexanone), Tetrahedron Letters (2017), doi: http://dx.doi.org/10.1016/j.tetlet.
2017.04.093
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Graphical Abstract
Leave this area blank for abstract info.
Valorization of Madagascar’s CNSL via the
synthesis of one advanced intermediate (3-
Pentadecylcyclohexanone)
Andrianarivo Irène Rahobinirina,a,b Maonja Finaritra Rakotondramanga,a Alexandra Berlioz-Barbier, c
Estelle Métay,d Voahangy Ramanandraibe a,b and Marc Lemaire. *a,d

1
Tetrahedron Letters
journal homepage: www.els evier.com
Valorization of Madagascar’s CNSL via the synthesis of one advanced intermediate
(3-Pentadecylcyclohexanone)
Andrianarivo Irène Rahobinirina,a,b Maonja Finaritra Rakotondramanga,a Alexandra Berlioz-Barbier, c
a,d
Estelle Métay,d Voahangy Ramanandraibe a,b and Marc Lemaire.∗
a Laboratoire International Associé Antananarivo-Lyon 1, Faculté des Sciences BP 906, Université d’Antananarivo, Madagascar.
b Laboratoire de Chimie et de Valorisation des Produits Naturels, Faculté des Sciences BP 906, Université d’Antananarivo, Madagascar.
c Centre Commun de Spectrométrie de Masse (CCSM), France
d Laboratoire CASYEN-ICBMS-UMR5246- Université Claude Bernard Lyon 1, France.
ARTICLE INFO
ABSTRACT
Article history:
Received
A unique advanced intermediate: 3-pentadecylcyclohexanone was synthetized from the crude
product which contained a mixture of cardanol, cardol and 2-methylcardol, which was
hydrogenated onto Pd/C at 80°C. From this alkylated cyclohexanone: C15 alkylated adipic acid,
caprolactam, caprolactone, were synthetized in high yields, such products may have many
potentially applications in polymer chemistry. The condensation of the 3-pentadecyl-
cyclohexanone and triethylene glycol in oxidative or reductive conditions gave aryl ether and
cyclohexyl ether, this may be a way to prepare intermediate for surfactant chemistry. Therefore
we show that Cashew Nut Shell Liquid (CNSL) may lead to numerous useful compounds thank
to the preparation of a unique advanced intermediate.
Received in revised form
Accepted
Available online
Keywords:
CNSL
Cyclohexanone
Cardanol
2009 Elsevier Ltd. All rights reserved
.
Synthesis

2
1. Introduction
CNSL was also used for the synthesis of resins with various
aldehydes or these materials were transformed into
polyurethane.9 Epoxide resins were also prepared using either the
phenol or the alkene groups to introduce the epoxide functions.1
Industrial ecology is one of the most important concepts
developed in the so call “green chemistry”. In industrial ecology
the waste of one factory should become the starting material of a
second factory. So use of starting material and energy and
ultimate waste production should be minimized.1 Fruit industry
appears to be one of promising areas for the development of such
concept. Indeed, fruit industry is collecting large amount of raw
materials and use only a fraction of the collected fruits. Peels,
hulls and in some case seeds are burned or landfill.2 Over the
world the production of Cashew Nuts is higher than 2.2 millions
of tons.3 These nuts contain 30% of kernel and 70% of Hulls.2
Cashew hulls could be easily extracted with hexane to give a
liquid with a very original composition including one of the rare
natural sources of non-polymerized aromatic rings (Fig 1).4
Indeed CNSL is clearly one of the best candidate for valorisation
and several recent articles and reviews have described its
application in different areas. Antibacterial and larvicidal
properties of CNSL, and in particular of derivatives of anacardic
acid and cardanol were demonstrated.5 Antioxidant properties of
CNSL constituents were also studied 6 and applications in curing
of natural rubber or as additive for biofuel were proposed.7
Oxidation of cardanol with peroxides allows the formation of
materials with good temperature stability and medium flame
retardant properties.8
Fig 1 Main constituents of the Cashew Nut Shell Liquid
Scheme 1 Preparation of 3-Pentadecylcyclohexanone from the CNSL mixture
Fig. 3. Main constituents of ethanol extract
0
5
10
15
20
Table 1. Results of UPLC – HRMS analysis coupled with a
high resolution mass spectrometer
Fig 2Chromatogramof (a) Malagasy CNSL, (b) decarboxylated CNSL, (c)
Mixture of Gallic acid and tannin.
[M-H]
m/z
Structure proposition
Ion Formula
C7H5O5
169.0142
Gallicacid

3
C8H7O5
183.0299
197.0455
939.1109
433.114
Methyl gallate
Syringicacid
2.4. Reduction of cardanol
C9H9O5
Firstly, we reduced pure cardanol using different catalysts and
hydrogen under pressure since the reduction of phenol may lead
to the formation of cyclohexanone which can be considered as a
useful advanced intermediate (Scheme 2). 14 Although the
aromatic ring could be easily reduced using ruthenium or
rhodium metal nanoparticles or colloids,15 we chose, to facilitate
the separation and the recycling of the catalyst, to use
commercially available transition metal on support.
C41H31O26
C21H21O10
C30H29O12
Penta-O-galloyl-D-glucose
Iso hemiphloin
Leufolin
581.1654
Finally, the aromatic ring of cardanol was transformed into
diacid, then the reaction with diamine via a 6 steps gave the
polyamides.
Attempts with silica or alumina as support for ruthenium
particles prove to be inefficient conversely ruthenium and
palladium onto hydrophobic support such as carbon were active
catalysts. Ruthenium catalysts clearly exhibited poor selectivity
toward the 3-Pentadecylcyclohexanone: at low temperature the
main product is the 3-pentadecyclphenol and at a higher
temperature both the aromatic ring and the ketone were reduced:
the two isomers of 3-pentadecylcyclohexanol are obtained as
major products. Conversely complete reduction of the aromatic
ring and few reduction of the ketone were observed when using
palladium even at 80 °C. 16
Although promising, these applications are still limited and
cardanol should be separated from cardol and others derivatives
and is mainly used as renewable source of alkylated phenol ring
This strategy suffers from the comparatively very low price of
the petro-sourced phenols. One of the main difficulties, when
working with agro-industry wastes, is linked to the complex
composition of the crude material with often significant seasonal
variations. From this general point of view, CNSL contain
aromatic compounds with one or two phenol groups, no or one
carboxylic group, no or one methyl group and finally a C15 alkyl
chain with one, two or three double bonds.
2.5. Reduction of cardol
Finally, we have reduced the cardol derivatives in similar
conditions and we were very pleased to observe that the main
product obtained was also the 3-Pentadecylcyclohexanone.
In this article we describe a strategy allowing the access to a
unique advanced intermediate (3-Pentadecylcyclohexanone,
Scheme 1) and then the preparation of several building blocks of
high potential for polymer science and technology.
2. Result and discussion
2.1. Extraction of CNSL
Although production of Cashew nut in Madagascar is
important and increasing 4660 metric tons/years, Malagasy
CNSL is not valorised for the moment. We have worked on hulls
obtained from cashew trees (Anacardium occidentale L.) of
Boeny Region, Madagascar. More precisely, using Soxhlet
extraction with hexane, we obtained 39 wt% of a dark brown
liquid from the crushed cashew hulls. The composition is given
above and contains mainly 4 families of products with only
difference at the number and the position of CC double bonds on
the alkenyl chains: Anacardic acid 71 % (1), Cardol 19 % (2),
Cardanol 4 % (3) and 2-Methyl cardol 1,2 % (4). Another
extraction of cashew nut shell residue by ethanol supplied 5.8%
of a mixture of gallic acid and tannin (Fig 3).
Scheme 2 Reduction of cardanol using different catalysts. Reactions
conditions: (a) H2, Ru/C (1 mol-%), Hexane, 20 Bar, rt, 5h; (b) H2, Ru/C (1
mol-%), Hexane, 20 Bar, 70°C, 5h; (c) H2, Pd/C(2 mol-%), Hexane, 30 Bar,
80°C, 3h.
These compounds and its derivatives are commonly used in
tannery, for the production of ink and as starting materials for
chemical industry. 12 As a consequence, we focused this study on
the valorization of anacardic derivatives.
2.2. Decarboxylation of CNSL
A way of simplifying the mixture of CNSL consists in
decarboxylating the anacardic acid derivatives following the
Tejas conditions in reflux of toluene.13 Nevertheless,
Antananarivo is located at a height of 1276 m, consequently the
boiling point of toluene is too low at this place to perform the
reaction in a reasonable speed. Therefore, we used the reflux of
xylene instead of toluene and we obtained a mixture of cardanol,
methyl cardol and cardol derivatives with 94 % yield.
Scheme 3 Hydrogenation of CNSL
This could be explained by the reduction of the resorcinol ring
into diketone then hydroxyl ketone, dehydration, followed by the
reduction of the CC double bond to give the cyclohexanone. In
this particular case, the 3-Pentadecylcyclohexanone was obtained
after chromatography purification with 36 % yield.
2.3. Synthesis and purification of 3-Pentadecylcyclohexanone
In order to obtain an even more simplified mixture by the
formation of cyclohexanone derivative, we reduced the
aromatic core and the alkyl chain. First of all, we separated the
cardanol derivatives from the cardol and methyl cardol using
chromatography (silica gel, hexane, ethyl acetate) with 80 %,
14,8 %, 1,1 % isolated yields respectively. These samples
contained 3-alkenyl phenol, 3-alkenyl methyl resorcinol and
3-alkenyl resorcinol with variations on the alkenyl chain.
Therefore it was possible to transform the two main products
of decarboxylated CNSL into a single product. The main
drawback of this method is the use of solvent with high
ecological impact (methylene chloride), nevertheless this is only
due to the poor solubility of the pure cardanol and cardol in
alkane. We have furthermore demonstrated a higher solubility of

4
the crude decarboxylated CNSL and the possibility of using
alkane as solvent for the reduction of the natural mixture (see
below).
second one, using the same amount of hydroxylamine
chlorohydrate in the presence of sodium hydroxide in ethanol a
yield of 94 % of the syn and anti oxime was obtained (Shedge et
al., 2005) 16. Similarly, for the second step, the Beckmann
transposition was firstly tested using 70 % sulfuric acid and such
conditions allowed the formation of the desired product with only
low yield and hydrolysis into the previous ketone was the main
reaction. On the opposite, the use of 1 mol /mol of 100 % sulfuric
allowed the formation of the two desired lactams (Scheme 5),
(white solid mp 81°C) with 61 % yield after purification by
chromatography.
2.6. Reduction of the decarboxylated Cashew Nut Shell Liquid
Attempt in reducing the crude cashew nut shell liquid directly
after decarboxylation was unsuccessful; this is probably due to
the poisoning effect of highly polar compounds similar to that
obtained by ethanol extraction (see above). Indeed after
elimination of such polar compounds by filtration through a pad
of silica (ethyl acetate 95% yield), the reduction was performed
in hexane and similar conditions that of pure cardanol.
2.7.3. Alkylated caprolactone
Caprolactone is an important monomer for the synthesis of
poly(esters). The alkylated cyclohexanone was treated with
m-CPBA in solvent at 25 C (Scheme 6, Method A), after
purification by extraction with sodium carbonate and
chromatography, 74 % yield of a white solid (mp 42 C). In order
to avoid the formation of large amount of m-chlorobenzoic acid
as by-product and the use of methylene chloride, we performed
the reaction using 30 % hydrogen peroxide in acetic anhydride
(Scheme 6; Method B), the desired lactone was obtained in 39 %
yield.
To validate the poisoning effect of polar molecules, a
reduction was performed with addition of 20 wt.% of crude polar
compounds obtained during the ethanol extraction (see above)
under hydrogen pressure with 1 mmol of 3-pentadecylphenol,
2 mol-% of Pd/C at 80°C. The conversion was in this case
incomplete.
Moreover it was possible to use hexane (or better heptane)
(Scheme 3) as solvent for this reaction with the mixture of
natural CNSL.
The purification of the crude product after reduction by
3-
chromatography
allowed
us
to
obtain
pure
Pentadecylcyclohexanone with 58 % (mp 43 °C) of yield but
more simply, recrystallizing in ethanol leaded to a white solid in
more of 90 % purity and with 70 % yield. Methyl cardol
derivatives are only partly reduced and are soluble in ethanol as
well as the major part of the isomers of 3-pentadecyl-
cyclohexanol. Therefore our strategy gave access to a unique
advanced intermediate with overall (two steps) yield of 67 %
from the crude Cashew Nut Shell Liquid. It was possible to
propose many potential synthetic applications for this alkylated
cyclohexanone, we have already evaluated some of them.
2.7. Potential applications of 3-Pentadecylcyclohexanone
2.7.1. Synthesis of alkylated adipic acid
The preparation of diacid from cyclohexanone, is an important
industrial process for the preparation of adipic acid.17 We
evaluated conditions similar to that already used for adipic acid
synthesis in order to obtain the diacid with C15 chain as pendant
group.
Scheme 5 Synthesis of alkylated caprolactam
Scheme 4 Synthesis of 3- pentadecyl-adipic acid
Scheme 6 Synthesis of alkylated caprolactone
The difficulty in using nitric acid in water and sodium nitrite
with a hydrophobic substrate such as 3-Pentadecylcyclohexanone
could be overcome by using acetic acid as co-solvent. We
obtained the desired products after hexane crystallizing as a
mixture 1/1 of two regioisomers with 81 % yield (Scheme 4)
(white solid mp 78°C).
2.7.4. Alkylated phenyl ether
Phenyl ethers are interesting building blocks as solvent and
potentially as surfactant or plasticizer. Generally, phenyl ethers
are obtained by Williamson type synthesis 19 or by aromatic
nucleophilic substitution catalysed either by copper 19 or
palladium.20 Although very useful, these reactions suffer from
several drawbacks such as production of salts as by-products, the
use of toxic solvent and/or expansive catalyst.
2.7.2. Alkylated caprolactam
Similarly, the preparation of caprolactam with pendant alkyl
chain could be performed by the same method used for
caprolactam itself. 18 Oxime could be prepared by using
hydroxylamine chlorohydrate then Beckman transposition was
performed in sulfuric acid. The first step was tested in two
conditions: the first one, using a solution of free hydroxylamine
(2 eq) in ethanol at 60°C that gave a low conversion. And a
More recently the use of oxidative alkylation of
cyclohexanone was proven to be an efficient alternative with
lower ecological impact.21 In this reaction the formation of ketal
or enol ether is followed by deshydrogenation over activated
palladium. The formed hydrogen was scavenged either by an
alkene or by air. 21

5
In the case of 3-Pentadecylcyclohexanone the difficulty is
linked to the high hydrophobicity of the substrate hardly
compatible with polar alcohol, nevertheless we performed the
reaction at 150°C, with the presence of an excess of triethylene
glycol and after 36 hours we isolated only 9 % of the desired
product (18) (Scheme 7).
This low isolated yield makes, (for the moment) the method
useless from a practical point of view. Therefore, we tested the
reductive alkylation following the conditions developed in Lyon
laboratory. The reductive alkylation 22 of 3-Pentadecyl-
cyclohexanone with triethylene glycol in a 1:5 molar ratio at
100 °C was performed (Scheme 8), as shown in Table 2.
Scheme 7 Synthesis of oxyethylen ether of 3-pentadecylphenol
In the reaction the competition between reduction of
cyclohexanone into cyclohexanol and the desired reductive
alkylation could be limited by using a large excess of the alcohol
and by limiting both the hydrogen pressure and the catalyst load.
Scheme 8. Synthesis of oxyethylen ether of 3-pentadecylcyclohexanol
Scheme 9 Examples of potential valorizations of CNSL via 3-Pentadecylcyclohexanone
Table 2. Reductive alkylation of the 3-Pentadecylcy-
clohexanone
Acknowledgments
Entry
Pressure (Bar)
Time (h)
Yield (%)[b]
This Project was financially supported by the Agence
Universitaire de la Francophonie (AUF).
1
2
3
4
40
14
22
28
16
48
55
57
58
30
Supplementary Material
20
40[c]
Supplementary data associated with…
References and notes
aCondition: molar ratio of 3-Pentadecylcyclohexanone/triethylene glycol =
1/5, Pd/C (5mol-%), 100 °C under hydrogen pressure.
bYields were determined on Column chromatography.
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1/10
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Although CNSL is, like most of the natural products and
agroindustry wastes, a complex mixture, we found a strategy
allowing the preparation of unique advanced intermediate in two
steps and with high yield. This 3-Pentadecylcyclohexanone has
structural similarity with the cyclohexanone which is a very
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7
• The synthesis of one advanced intermediate is proposed.
• The hydrogenation of the crude cardanol-cardol mixture gave the corresponding
ketone.
• The 3-Pentadecylcyclohexanone has structural similarity with the cyclohexanone
• Di-acid, lactam, lactone and ethers were obtained in few steps and good yields.