April - June 2011 64 JLST Vol. 43 No.

2
ABSTRACT
Liquid wax esters are industrially important
oleochemicals having applications in the cosmetic
and personal care product. In an attempt to develop
some castor-based industrial product, the present
study described the synthesis of undecylenic acid-
based liquid wax esters followed by evaluation of
their physicochemical properties vis-a-vis the jojoba
oil, the only natural wax esters used by the industry.
Looking at the structural features of jojoba oil, three
different types of mixed fatty alcohols based on
vegetable oils, namely high oleic sunflower oil (HOSO),
mustard oil (MO) and castor oil (CO) were esterified
to undecylenic acid. Esterification was conducted either
by usi ng Lewi s aci di c i oni c l i qui d, chol i ne
chloride.2ZnCl
2
or by using PTSA. All the products
were evaluated for different physicochemical properties
and compared with those of jojoba oil.
KEYWORDS: Wax ester, undecylenic acid, castor oil,
mustard oil, high oleic sunflower oil, jojoba oil, ionic
liquid.
INTRODUCTION
Wax esters are esters of long chain carboxylic
acids and long chain alcohols, and are an important
class of oleochemicals that are widely used as base
materials in cosmetics, pharmaceuticals, lubricants,
paints, wood coatings and perfumery products
1-4
.

Many
attractive features such as biodegradability, non-toxicity
and preparation from vegetable oils make wax esters
industrially important chemicals. Wax esters are solid
or liquid depending on the kind of fatty acid or fatty
alcohol present in it. Specialty liquid wax esters such
as jojoba and sperm whale oil have wide industrial
applications as premium lubricants, parting agents,
anti foaming agents and in cosmetics. But due to the
ban imposed by the Government of USA on the use
of sperm whale oil in 1974, cosmetic and personal
care industries are totally relying on jojoba oil.
Jojoba oil is the liquid wax produced in the seed
of the jojoba (Simmondsia chinesis) plant, a shrub
native to North and South America. Jojoba seed
contains about 50% of liquid wax esters composed
mainly of straight chain monoester having chain length
in the range of 38 to 46 carbon atoms
5
. Structurally
though it is similar to sperm whale oil, but does not
possess fishy odor. Synthesis of jojoba oil is difficult
because of its unique feature. There are reports of
synthesis of jojoba analogue and also their chemical
modification
6,7
. It does not oxidize or become rancid
and does not breakdown under high temperatures
and pressures. The stability shown by jojoba oil makes
it especially useful for body and skin care applications.
Thus, it is worthwhile to synthesize a jojoba oil
analogue based on available resources.
10-Undecylenic acid (UDA) is the well known
pyrolysis product of castor oil having antifungal,
antibacterial and antiviral activities
8
. UDA, in general
is extensively used for the preparation of Nylon 11 or
Rilsan fibers produced from -aminoundecanoic acid
9
.
UDA is an interesting renewable raw material readily
used i n i nsecti ci dal , fungi ci dal and perfume
formulations
10-11
. It is also used as precursor for the
synthesis of antitumor compounds and antibiotics
12
.
UDA is also used as precursor for the synthesis of a
host of insect pheromones
13
. Despite potential, UDA
has not been exploited appropriately in India. In an
effort to develop industrially useful materials out of
castor oil, the present research work explored the
possibility of preparing UDA-based liquid wax ester,
mimicking jojoba oil.
The present study describes the preparation of
liquid wax esters, wherein fatty alcohol mixtures,
obtained from vegetable oils are esterified to UDA.
Looking at the structural features of jojoba oil, it is
planned to take mixed fatty alcohols based on
vegetable oils, namely high oleic sunflower oil (HOSO),
mustard oil (MO) and castor oil (CO). Different physico-
chemical properties of the synthesized liquid wax
esters, such as iodine value, acid value, fatty acid
composition, refractive index etc are evaluated and
compared with jojoba oil. The synthesized products
are also evaluated for their antimicrobial activities and
compared with jojoba oil.
Synthesis of Undecenoic Acid-based Liquid Wax Esters
A Shivaraju, R B N Prasad and Sanjit Kanjilal
*
Centre for Lipid Research, Indian Institute of Chemical Technology,
Uppal Road, Hyderabad 500 007
*To whom correspondence should be addressed
E-mail: sanjit@iict.res.in
April - June 2011 65 JLST Vol. 43 No. 2
MATERIALS AND METHODS
Materials
10-Undecylenic acid, p-toluene sulfonic acid and
NaBH
4
was purchased from M/s SD fine chem,
Mumbai, India. Mustard and castor oil was purchased
from the local market and high oleic sunflower oil was
a generous gift of M/s Advanta India Ltd, Hyderabad,
India. The silylating agent, bis-[N,O-trimethylsilyl]
trifluoroacetamide (BSTFA) was purchased from Sigma
(St. Louise, MO, USA). Silica gel (60-120 mesh) for
column chromatography was purchased from M/s
Acme Synthetic Chemicals (Mumbai, India) and pre-
coated TLC plates (silica gel 60 F254) were purchased
from Merck (Darmstadt, Germany). All solvents,
purchased from M/s SD fine chem. (Mumbai, India)
were of highest grade of purity and were used without
further purification.
Methods
Instrumental analysis: The fatty acid compositions of
studied oils are determined using GC after derivatizing
them to fatty acid methyl esters (FAME). The analysis
was performed on Agi l ent 6890 seri es gas
chromatograph equipped with a FID and the capillary
column DB-23 (30m 0.25 mm 0.5 m). The oven
temperature was programmed as: 2 min at 160C,
5C min-1 to 230C and finally maintained at 230C
for 20 min. The carrier gas, N
2
flows at 1.5 ml/min.
The injector and detector temperature was maintained
at 230 and 250C respectively and split ratio was
maintained at 50:1. The compositions of fatty alcohols
(FA) are also determined by GC after converting them
to their silyl derivatives. The qualitative and quantitative
analysis of silylated fatty alcohols and wax esters
were determined using GC-MS and GC. GC-MS was
carried out with Agilent 6890 N
2
gas chromatograph
connected to Agilent 5973 mass spectrometer (Palo
Alto, USA) and GC on HP 6850 Series gas
chromatograph equipped with a FID detector. The
GC-MS detection was performed at 70 eV (m/z 50-
550; source at 230C and quadruple at 150C) in the
EI mode attached with HP-1 ms capillary column (30
m 0.25 mm 0.25 m). The oven temperature was
programmed for 2 min at 150C, raised to 300C at
10C min
-1
and finally maintained at 300C for 15 min.
The carrier gas, He flows at 1.0 ml/min and the split
ratio is maintained at 50:1. Structural assignments
were based on interpretation of mass spectrometric
fragmentation and confirmed by comparison of
retention times as well as fragmentation pattern of
authentic compounds. The GC was performed in
HP-1 capillary column (30m 0.25 mm 0.5 m) and
the oven temperature programming is similar to that
of GC-MS with the injector and detector temperature
maintained at 300 and 325C. Acid value, iodine
value and refractive index are determined as per
AOCS methods
14-16
. Viscosity was determined as per
ASTM method
17
. Density was determined using Anton
Paar Densitymeter (DMA 4500M).
Preparation of fatty acid methyl esters (FAME) of
vegetable oil: Vegetable oil (50.0 g) was taken in 100
ml of 2% H
2
SO
4
in methanol and refluxed for 4.0 hr.
After 4 hr, methanol was evaporated and FAME was
extracted with hexane. The organic layer was washed
with water, dried over anhydrous Na
2
SO
4
, concentrated
and analyzed by GC. The fatty acid composition of
the three studied oils, high oleic sunflower oil (HOSO),
mustard oil (MO) and castor oil (CO) are given in
Table 1.
Reduction of vegetable oil-based fatty acid mixture to
fatty alcohols: Reduction of fatty acid methyl esters to
fatty alcohols were carried following a reported
method
18
. High oleic sunflower oil FAME (average
molecular wt 296; 10 g; 0.0338 mol) was solubilized
in 40 ml of tert-butanol followed by the addition of
NaBH
4
(2.55 g; 0.067 mol) and the reaction mixture
was refluxed. In this stirred reaction mixture, methanol
(8 ml) was added over a period of one hour. After
completion of methanol addition, the reaction mixture
was refluxed overnight. Progress of the reaction
mixture was monitored by TLC. After 12 hr, water was
added for quenching the reducing agent and the
reaction mixture was evaporated in the rotary
evaporator to remove tert-butanol and methanol. The
unconverted FAME was saponified as per AOCS
method
19
. Briefly, 15 g of KOH was solubilized in 10
ml of water and 5 ml of this alkaline solution was
added to 30 ml of ethanol. The combined alkaline
aqueous ethanolic solution was added to the reaction
mixture and refluxed for 1 hr. After 1 hr, the reaction
mixture was concentrated in the rotary evaporator
and extracted thrice with ethyl acetate. The combined
ethyl acetate layer was washed with water till neutral,
dried over anhydrous Na
2
SO
4
, concentrated and dried
under vacuum to get 4.5 g (50.0%) of fatty alcohol
mixture. The mixture was analyzed by GC-MS and
GC after silylation using BSTFA
20
.
Castor oil FAME (average molecular wt 312; 10 g;
0.0325 mol) was solubilized in 40 ml of tert-butanol
followed by the addition of NaBH
4
(2.42 g; 0.064 mol)
and methanol (8 ml) and similar procedure was
conducted as mentioned above. About 5.62 g (62.0%)
of fatty alcohol mixture was obtained, which was
analyzed by GC-MS and GC after silylation.
Mustard oil FAME (average molecular wt 327; 10 g;
0.03 mol) was solubilized in 120 ml of tert-butanol
April - June 2011 66 JLST Vol. 43 No. 2
followed by the addition of NaBH
4
(2.88 g; 0.076 mol)
and methanol (25 ml) and similar procedure was
conducted as mentioned above. About 3.73 g (41.0%)
of fatty alcohol mixture was obtained, which was
analyzed by GC-MS and GC after silylation.
Esterification of mixture of fatty alcohols with UDA:
Esterification of mixture of fatty alcohols, obtained
from HOSO and MO with UDA was carried out in
presence of Lewis acidic ionic liquid, choline
chloride.2ZnCl
2
4
. This is a novel method developed in
our laboratory and has many advantages over the
existing methods. However, this method could not be
taken for the esterification of CO-based fatty alcohols
with UDA due to the dehydration of the secondary
hydroxyl moiety of fatty alcohols. In this case, the
esterification is conducted using PTSA.
A mixture of HOSO fatty alcohols (2 g; 0.0074
mol), UDA (1.37 g; 0.0074 mol) and Ionic liquid (3.08
g, 0.0074 mol) was stirred at 110
o
C for 12 hrs. The
progress of reaction was monitored by TLC. After
completion of this reaction the reaction mixture was
extracted with ethyl acetate (30 ml x 4) for separation
of ionic liquid and product. This crude product was
loaded in silica gel column and eluted with hexane to
get pure wax ester (2.32 g clear oil; isolated yield,
72.04%).
Similarly, a mixture of mustard alcohol (2 g,
0.006 mol), UDA (1.27 g, 0.006 mol) and ionic liquid
(2.84 g, 0.006 mol) was stirred at 110
o
C for 12 hr. The
progress of reaction was monitored by TLC. After
completion of this reaction the reaction mixture was
extracted with ethyl acetate (30 ml x 4) for a separation
of ionic liquid and product. This crude product was
loaded in silica gel column and eluted with hexane,
hexane: ethyl acetate (99:1) to get pure wax ester
(1.92 g clear oil; isolated yield, 61%).
Castor oil fatty alcohols (2 g; 0.007 mol) and
UDA (1.25 g; 0.007 mol) was taken in a solvent free
medium and 0.5% PTSA (10 mg) was added into the
reaction mixture as an esterification catalyst and
stirred at 120C. The progress of reaction was
monitored by TLC. After 8 hr the reaction was extracted
with ethyl acetate, washed with water, dried over
anhydrous Na
2
SO
4
and concentrated to obtain 3.62 g
of crude product. The crude mixture was purified by
column chromatography by loading the entire amount
on silica gel and eluting with hexane: ethyl acetate
(96:4) to obtain 2.1 g (yellowish oil; isolated yield,
68.2%) of pure wax ester.
RESULTS AND DISCUSSION
Almost all the chemicals derived from castor oil
have immense industrial applications. 10-Undecylenic
acid (UDA) is obtained during high temperature
pyrolysis of castor oil. UDA possess two terminal
functional groups and is widely used in the food,
perfumery and other chemical industry. In the present
work, an attempt was made to synthesize liquid wax
esters based on UDA. The present work was
undertaken due to wide industrial applications of liquid
wax esters, mimicking jojoba oil.
Presently, jojoba oil is the only natural liquid wax
ester used industrially. It consists of a mixture of
esters of long chain fatty alcohol and long chain fatty
acids, mainly C38:2, C40:2, C42:2, C44:2 and C46:2.
The major esters among them are C40:2 and C42:2.
All these components are formed from C18:1, C20:1,
C22:1 and C24:1 carboxylic acids and alcohols
21
. To
match these structural features of jojoba oil, three
different vegetable oils, namely high oleic sunflower
oil (HOSO), mustard oil (MO) and castor oil (CO)
were chosen based on their fatty acid composition. All
these oils are rich in monounsaturated fatty acids.
The fatty acid composition of these oils (Table 1)
indicates that the content of monounsaturated fatty
acid in HOSO, MO and CO is 84, 65 and 89%
respectively. Fatty acid mixtures obtained from these
vegetable oils are reduced to fatty alcohols. The
compositions of fatty alcohols, obtained from three
studied vegetable oils are given in Table 1. A marginal
change in composition of fatty alcohol was observed
when compared with the composition of fatty acids
characteristic to the corresponding oil. Thus after
reduction, the content of monounsaturated fatty
alcohols in HOSO, CO and MO is 88.3, 100 and 67%
respectively.
TABLE 1
Composition of Fatty Acid (FAME) and Fatty Alcohols
(FA) of Castor, Mustard and High Oleic Sunflower Oil
Fatty
HOSO (wt%) CO (wt%) MO(wt%)
acid
FAME FA FAME FA FAME FA
16:0 4.0 4.3 1.1 - 2.1 5.7
18:0 2.6 3.2 1.3 - 1.1 1.4
18:1 84.0 88.3 4.1 - 10.6 15.9
18:2 7.9 4.2 4.4 - 14.7 7.7
18:3 0.3 - - - 12.0 14.3
18:1(OH) - - 88.7 100 - -
20:0 0.2 - - - 3.6 0.8
20:1 0.3 - - - 3.6 5.8
22:0 0.7 - - - 1.4 1.2
22:1 - - - - 49.5 45.6
24:0 - - 0.4 - 1.4 0.3
April - June 2011 67 JLST Vol. 43 No. 2
Esterification of mixture fatty alcohols obtained
from HOSO and MO with UDA was carried out in a
Lewis acidic ionic liquid, choline chloride.2ZnCl
2
. The
methodology was developed in our laboratory for the
synthesis of a range of mono and diesters. It has
several advantages over other reported methods
4
.
However, the methodology was not attempted for the
esterification of mixture of fatty alcohols with acid or
vice versa. In the present study, this was attempted
for the synthesis of mixture of wax esters from HOSO
and MO fatty alcohol mixture.
Castor oi l i s ri ch i n ri ci nol ei c aci d, 12-
hydroxyoctadec-9-enoic acid. When castor-based fatty
alcohols are attempted to be esterified to UDA in
presence of ionic liquid, several side products were
produced. This is due to the dehydration of ricinoleic
acid catalyzed by the studied ionic liquid. Hence,
castor oil-based wax esters were prepared by
traditional method of using 0.5% PTSA. The
composition of all these three wax esters were
analyzed by GC-MS and GC (Figure 1) and are given
i n Tabl e 2. Resul ts obtai ned i ndi cate that
oleoylundecenoate (C29:2) and erucylundecenoate
(C33:1) are the major component in the wax ester
mi xture based on HOSO and MO, whereas
ricinoleoylundecenoate (C29:2-OH) is the exclusive
product formed in the CO-based wax ester.
TABLE 2
Composition of Wax Ester Obtained After
Esterification of UDA & Fatty Alcohols Mixture
Based on HOSO, CO and MO
HOSO- CO- MO-
UDA UDA UDA
wax wax wax Wax Ester
ester ester ester
(wt%) (wt%) (wt%)
Palmitoylundecenoate 4.8 - 4.6
Oleoylundecenoate 95.2 - 37.0
*
Ricinoleoylundecenoate - 100 -
Eicosenoyllundeceonate - - 6.4
Erucylundecenoate - - 50.2
Tetracosenoylundecenoate - - 1.7
*
Combined wt% of stearoyl-, oleyol-, linoleoyl- and
linolenoylundecenoate
Different physico-chemical parameters, like acid
value, iodine value and refractive index of the three
prepared wax esters were determined and compared
with those of jojoba oil. Results obtained are
summarized in Table 3. All these properties of the
three prepared liquid wax esters matched well with
those of jojoba oil.
Fig. 1: GC chromatogram of three studied wax esters:
(A) HOSO-UDA, (B) MO-UDA and (C) CO-UDA.
TABLE 3
Comparative Characterization of UDA-based Wax
Esters with Jojoba Oil
Physico- HOSO- CO- MO-
chemical Jojoba UDA UDA UDA
para- oil wax wax wax
meters ester ester ester
(wt%) (wt%) (wt%)
Iodine Value 88.2 113.9 97.0 104.8
Acid Value 1.5 2.0 2.0 2.0
Refractive
index 1.4629 1.4522 1.4569 1.4577
Density 0.8617 0.9033 0.8921 0.8767
Viscosity 24.97 21.07 18.51 15.69
April - June 2011 68 JLST Vol. 43 No. 2
In conclusion, three different liquid wax esters, based
on high oleic sunflower, mustard and castor oil fatty
acid mixtures were prepared and their physicochemical
properties were evaluated. The iodine value, acid
value and refractive index of the three prepared liquid
wax esters matched well with that of jojoba oil. The
terminal double bond of UDA in these wax esters can
be functionalized further in order to have better
emollient property, increased oxidative stability and
better lubricant properties.
ACKNOWLEDGEMENT
Authors are grateful to the Indian Council of Agricultural
Research (National Agricultural Innovative Project) for
the financial grant.
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