Synthesis and characterization of aurantiol schiff base, relationship between synthesis time and some physical properties

Article abstract of DOI:10.13005/ojc/340142

Aurantiol or hydroxycitronellal-methyl anthranilate schiff base was a common compound added in the manufacture of fragrance. The addition of aurantiol to the fragrance, made the fragrance more stable and the resulting odor can last longer. Generally aurantiol was prepared by reflux technique with stirring and addition of acid catalyst, which then was continued by recrystallization to purify the resulted aurantiol. This method was ineffective and required a high cost, so it needed a more effective and efficient manufacturing techniques, namely simple condensation technique. This technique consisted of two steps: the synthesis step, and the characterization. The synthesis step was began by weighing of the raw material were hydroxycitronellal and methyl anthranilate. The synthesis of aurantiol was carried out by heating at 90±5 °C, and with variation of synthesis time for 15 min, 30 min, 1 h, 2 h, 3 h, and 4 hours. The characterization included chemical composition, organoleptic test, refractive index, density, specific gravity determination. Organoleptic tests included odor and color test. The measurement of refractive index was performed by refractometer, the chemical composition was performed by gas chromatography-mass spectrometer, while density and specific gravity were performed by pycnometer. From the experimental results, we got the optimum synthesis time that was between 30 min. to 1 h, with aurantiol products of 77.57%. In this optimum condition, the resulted aurantiol had odor test results: floral balsamic, sweet, orange blossom; color test: light yellow to greenish yellow; and refractive index, density, specific gravity were 1,543, 1.052 g/mL, 1,054 respectively. Based on the experimental results, it can be concluded that the synthesis of aurantiol with simple condensation technique has been successfully done, with the highest aurantiol yield of 77.57% with optimum synthesis time of 30 minutes to 1 hour. Therefore, this optimum condition can be used as a reference for the synthesis of aurantiol on an industrial scale.

Full text of DOI:10.13005/ojc/340142

ISSN: 0970-020 X
CODEN: OJCHEG
018, Vol. 34, No.(1):
Pg. 394-400
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
2
www.orientjchem.org
Synthesis and Characterization of Aurantiol Schiff Base,
Relationship Between Synthesis Time and Some
Physical Properties
1
1
2
CANDRA IRAWAN , SUCI INDRYATI , ENDANG SRI LESTARI ,
3
1
ARINZANI HIDANINGRUM and SUPRIYONO *
1
Department of Chemical Analysis, Politeknik AKA Bogor, Bogor 16154, Indonesia.
2
Department of Industrial Waste Treatment, Politeknik AKA Bogor, Bogor 16154, Indonesia.
3
PT. Nilam Widuri, Bogor Indonesia.
*
Corresponding author E-mail: supriyono272@gmail.com
http://dx.doi.org/10.13005/ojc/340142
(Received: Octuber 24, 2017; Accepted: Novmeber 25, 2017)
ABSTRACT
Aurantiol or hydroxycitronellal-methyl anthranilate schiff base was a common compound
added in the manufacture of fragrance. The addition of aurantiol to the fragrance, made the
fragrance more stable and the resulting odor can last longer. Generally aurantiol was prepared by
reflux technique with stirring and addition of acid catalyst, which then was continued by
recrystallization to purify the resulted aurantiol. This method was ineffective and required a high
cost, so it needed a more effective and efficient manufacturing techniques, namely simple
condensation technique. This technique consisted of two steps: the synthesis step, and the
characterization. The synthesis step was began by weighing of the raw material were
hydroxycitronellal and methyl anthranilate. The synthesis of aurantiol was carried out by heating
at 90±5 ꢀC, and with variation of synthesis time for 15 min, 30 min, 1 h, 2 h, 3 h, and 4 hours. The
characterization included chemical composition, organoleptic test, refractive index, density, specific
gravity determination. Organoleptic tests included odor and color test. The measurement of
refractive index was performed by refractometer, the chemical composition was performed by
gas chromatography-mass spectrometer, while density and specific gravity were performed by
pycnometer. From the experimental results, we got the optimum synthesis time that was between
30 min. to 1 h, with aurantiol products of 77.57%. In this optimum condition, the resulted aurantiol
had odor test results: floral balsamic, sweet, orange blossom; color test: light yellow to greenish
yellow; and refractive index, density, specific gravity were 1,543, 1.052 g/mL, 1,054 respectively.
Based on the experimental results, it can be concluded that the synthesis of aurantiol with simple
condensation technique has been successfully done, with the highest aurantiol yield of 77.57%
with optimum synthesis time of 30 minutes to 1 hour. Therefore, this optimum condition can be
used as a reference for the synthesis of aurantiol on an industrial scale.
Keywords: Schiff base, Aurantiol, Hydroxycitronellal, Methyl anthranilate, Fragrance.
This is an
.0 International License (https://creativecommons.org/licenses/by-nc-sa/4.0/ ), which permits unrestricted
NonCommercial use, distribution and reproduction in any medium, provided the original work is properly cited.
Open Access article licensed under a Creative Commons Attribution-NonCommercial-ShareAlike
4

SUPRIYONO et al., Orient. J. Chem., Vol. 34(1), 394-400 (2018)
395
INTRODUCTION
the fact that Schiff base can improve chemical
stability and resilience of fragrance blends. There
are many types of Schiff base used in the fragrance
industry, including jasmea, verdantiol, cyclantine,
indolene, helioforte aquanhtral, vertosine aqrumea
ligantraal, agrea, decimea, nonimea, ocmea,
isonomilat, amandolene, canthoxalia, acaciol, and
most often used in the industry is aurantiol, the schiff
Fragrance is a mixture of several
compounds that each compound works in
accordance with its properties to produce aromatic
1
-3
compounds.
Important properties of fragrance
include volatility, polarity, and stability. Volatility is
a key element in combining aromatic compounds.
High volatile materials will evaporate first, top notes
in perfumes, while materials with moderate volatility
base formed from a mixture of hydroxycitronellal
8
and resistance are called modifiers or middle notes, and methyl anthranilate.
and materials with low volatility are base notes or
4
bottom notes. Ones of the compounds added to
Aurantiol has the IUPAC nama: methyl-N-
,7-dimethyl-7-hydroxyoctyliden anthranilate, and
the fragrance to produce qualified fragrance is a
Schiff base. Schiff base is a compound formed from
condensation reaction between aldehyde and
3
several trade names such as aurantiol, auriol,
auranol, auralva, anthralal, aurangeol, aurantine,
5
-6
primary amine and produce water as byproduct.
Amines commonly employed in the fragrance and bigariol. Aurantiol has a molecular formula C H NO ,
18
27
3
4
industry are methyl anthranilate and ethyl so the molecular weight of 305.43 g/moL.
anthranilate, whereas aldehyde compounds
commonly used in the fragrance are alkyl or
aldehyde aromatics, terpen aldehydes, such as
In this study, we prepared aurantiol by
simple condensation technique with various
syntheses times. The optimum synthesis time was
7
hydroxycitronellal.
The reaction of Schiff base formation investigated and will be discussed here in.
2
as follows:
In general, methyl anthranilate produce a
schiff base in the form of solid or yellow viscous
liquid.The reaction of the formation of schiff base is
usually not perfect, so that the color of schiff base
does not become dark. Schiff base has a large
molecular weight compared to other fragrance
compounds, so the Schiff base is difficult to dissolve
in water and has good resistance. If there are
aldehyde and methyl anthranilate, it will react
spontaneously to form schiff base, and water as a
by-product, resulting in turbidity and separated into
two phases. One method used to remove a by-
product of water is by vacuum at high temperature
EXPERIMENTAL METHODS
4,7
and atmospheric pressure.
The experimental methods consisted of
two steps: the synthesis step, and the characterization.
Sell (2006) argues that the importance of The synthesis step was begun by weighing of raw
Schiff base in the fragrance industry is based on materials that were hydroxycitronellal and methyl

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SUPRIYONO et al., Orient. J. Chem., Vol. 34(1), 394-400 (2018)
anthranilate. The aurantiol synthesis was carried
out at a temperature of about 90±5ꢀC with
modification of time for 15 min, 30 min, 1 h, 2 h, 3 h,
and 4 hours. The characterizations consisted of
chemical composition, organoleptic tests, refractive
index, density and specific gravity determination.
Organoleptic tests included odor and color test by
Flavor & Texture Profile test method. Measurement
of refractive index was using refractometer, density
and specific gravity using pycnometer, and chemical
composition using Gas Chromatography-Mass
9
Spectrometer (GC-MS).
Table. 1: Analysis condition of GC-MS
Description
GC-MS Type
Agilent Technologies 5975C inert MSD
Column
Polar capillary column: HP-5 5% Phenyl Methyl Siloxan
Length = 30 m; Internal diameter = 0.25 mm; film thickness = 0.25 μm
Carrier gas
Helium
Carrier gas pressure
Detector
7,05 Psi
Mass spectrometer detector
Injector temperature
Injection volume
Injection technique
Split ratio
100 ꢀC
0,2 µL
Split
80 : 1
Temperature program (column) :
Initial temperature
Temperature rate
Final temperature
Interval
100 ꢀC, hold for 5 min.
15 ꢀC/minute
250 ꢀC, hold for 5 min.
20 min.
Density and specific gravity were calculated by the following formula:
1) RESULTS AND DISCUSSION
(
Synthesis of Aurantiol
Where: (ρ)
M
V
: density (g/mL)
: mass (g)
: volume (mL)
Aurantiol was obtained by reacting
hydroxycitronellal and methyl anthranilate, with a
simple condensation technique at (90 ± 5) ꢀC with
synthesis time of 15 min, 30 min, 1 h, 2 h, 3 h and 4
h, respectively. The result of the formation of
aurantiol with various synthesis times were as
shown in Figure. 1.
2)
Where: SG
: Specific gravity
: The density of the
ρ compound
compound (g/mL)
ρ water : Water density (g/mL)
The composition of the constituent
compound was determined using Gas
Chromatography-Mass Spectrometer (GC-MS),
which aurantiol 10% in ethanol was injected, then
the result of aurantiol fragmentation was determined
by the existing library. The condition of GC-MS as
in Table 1.
Fig. 1. Color of aurantiol product with various
synthesis time: a) 15 min, b) 30 min, c) 1 h, d) 2 h,
e) 3 hours, f) 4 hours

SUPRIYONO et al., Orient. J. Chem., Vol. 34(1), 394-400 (2018)
397
In addition to speed up the reaction, and separated into two phases.The aurantiol
10
heating also serve to eliminate byproducts of water formation reaction was as follows:
and to prevent the formation of a turbid aurantiol
Fig 2. GC-MS chromatogram of aurantiol with 15 minute synthesis time

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SUPRIYONO et al., Orient. J. Chem., Vol. 34(1), 394-400 (2018)
To prove that aurantiol was actually
and methyl anthranilate peaks at 6.367 and 7.268
minutes, respectively. This showed that the
aurantiol formation reaction was an equilibrium
reaction, so to increase the amount of aurantiol can
be done by evaporating water so that the
equilibrium shifted to the right. The results of
aurantiol analysis with GC MS at various synthesis
times were as follows:
formed, an analysis with GC-MS was performed.
Based on GC-MS chromatogram in figure 2, it was
seen that the aurantiol peak was at 14.773 and
1
5.441 minutes. The presence of two aurantiol
peaks indicated that aurantiol had 2 isomers namely
11
d-aurantiol and l-aurantiol , so total aurantiol was
the sum of d-aurantiol and l-aurantiol. In addition
to the aurantiol peak, there were also hydroxycitronellal
Table. 2: Results of aurantiol analysis with GC MS
Synthesis Times
% Area – GC Yield
Methyl anthranilate
Hydroxycitronellal
Aurantiol
1
3
1
2
3
4
5 min.
0 min.
h
h
h
h
11.61
9.53
10.00
8.36
9.29
9.45
14.86
12.90
12.96
25.68
20.67
24.43
73.53
77.57
77.04
65.95
70.03
66.12
Characterization of Aurantiol
OdorTest
One of the physical tests for checking the
quality of aurantiol was the odor test. The odor test
was performed by six trained panelists. The odor
test results were shown in Table 3.
The odor of aurantiol came from the
constituent compounds which were aldehyde and
amine. Floral odor came from aldehyde compounds
in the form of hydroxycitronellal while sweet and
orange blossom odor was obtained from methyl
anthranilate. The longer synthesis time of aurantiol,
the amount of citronellal it became less so that the
odor of floral it became disappear, on the contrary
the longer synthesis time, the amount of methyl
anthranilate it became more so that the odor of
Fig. 3. The relationship between aurantiol yield
and synthesis time
Table. 3: Result of odor test of Aurantiol
Synthesis times
Odor
1
3
5 min.
0 min.
Floral, sweet, orange blossom
Floral balsamic, sweet, orange blossom,
Floral green, sweet, orange blossom,
Floral, orange blossom, sweet (more jasmin)
Floral, orange blossom, sweet, tuberose
Floral, orange blossom
1
2
3
4
h
h
h
h

SUPRIYONO et al., Orient. J. Chem., Vol. 34(1), 394-400 (2018)
399
orange blossom became dominant. Considered
factor in the odor test of fragrance or fragrance raw
materials was the volatility. High volatile materials
will evaporate first, top notes on perfume, while
materials with the medium volatility and resistance
were called modifiers or middle notes, and materials
with the lowest volatility or most durable were base
notes or bottom notes. In aurantiol, the top note odor
was floral, the middle note was sweet, and the
bottom note was orange blossom. With synthesis
time of 30 min. was formed a floral balsamic odor,
while with 1 h synthesis time was formed a floral
green odor, derived from hydroxycitronellal
reactants. With 2 h synthesis time, there was
Based on table 4 above, it was seen that
aurantiol made with synthesis time of 15 min. 30
min. and 1 h produced a light yellow color, while
with a longer synthesis time of 2 hours, 3 hours and
4
h produced a darker color.
Table. 4: Results of aurantiol color test
Synthesis time
Color
1
3
1
2
3
4
5 min
Light yellow
Light yellow – greenish yellow
Greenish yellow
Dark yellow
0 min
h
h
h
h
Therefore it can be concluded that the
longer synthesis time, the top note odor will be lost
so that the remaining odor was the bottom note odor
that was orange blossom.
Orange
Orange
Refractive index, density and specific gravityTest
The measurement results of refractive
ColorTest
index, density and specific gravity of aurantiol as
shown in table 5 below. According to Panten (2002),
The color test was also a physical test that
becomes an important parameter of aurantiol
formation. The color test was performed by a trained hydroxycitronellal density was 0.9220 g/mL, methyl
panelist, and obtained results as in Table. 4. anthranilate was 1.1682 g/mL, and aurantiol was
Fig. 3. The relationship between refractive index, density, specific gravity and synthesis times

4
1
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SUPRIYONO et al., Orient. J. Chem., Vol. 34(1), 394-400 (2018)
From the observation data above, it product, in which methyl anthranilate had the biggest
1
2-13
.01 g/mL.
was seen that the longer synthesis time generated
aurantiol with greater refractive index, density, and
specific gravity. This was due to the increasing
quantity of methyl anthranilate in the aurantiol
density. So it can be concluded that the duration of
synthesis time was directly proportional to the
refractive index, density and specific gravity of the
aurantiol product.
Table. 5: Refractive index, density and specific grafity of Aurantiol at various synthesis times
Synthesis time
Refractive index
Density, g/mL
Specific gravity
1
3
1
2
3
4
5 minutes
0 minutes
hour
hours
hours
1.536
1.539
1.540
1.540
1.541
1.542
1.051
1.052
1.052
1.052
1.054
1.055
1.053
1.054
1.054
1.054
1.056
1.057
hours
CONCLUSION
to 1 hour can be used as a reference for the synthesis
of aurantiol on an industrial scale.
Based on the results of this study, it can be
concluded that the synthesis of aurantiol with simple
condensation technique has been successfully
done, with the highest aurantiol yield of 77.57%
with an optimum synthesis time of 30 minutes to 1
hour. The longer synthesis time, it will produce
aurantiol products with darker colors and greater
refractive index, density and specific gravity.
Therefore, this optimum synthesis time of 30 minutes
ACKNOWLEDGEMENT
The authors wish to thank to Politeknik
AKA Bogor, Ministry of Industry of Indonesia for
providing the research fund. Partial support from
PT. Nilam Widuri for GC-MS measurements is also
acknowledged.
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