Directed Study of Abietic Acid Reaction in Pine Rosin under Non - Precious - Metal Catalyst

Abstract

Pine rosin of Pinus merkusii Jung at de Vriese is produced industrially from a distillation process of pine sap. The high total Indonesian production leads the primary derivatization strategy into several derivates to fulfill the market demand. Abietic acid (AA) is a major compound in pine rosin, used as the object of observation in this study. The general methodology for transformation reported involves using palladium (Pd) and platinum (Pt)-based catalysts. Both are precious metal catalysts to proceed with oxidative dehydrogenative-aromatization of the rosin. The synthesized product provides dehydroabietic acid (DHA) derivatives in high yield. This paper reports that non-precious metal-based catalysts such as iron (Fe), zinc (Zn), or copper (Cu) with iodine (I 2) were applied to deliver the reaction by steam cracking without nitrogen (N 2) and oxygen (O 2) for economical, efficient, and greenway's catalyst. It was found that a similar product was isolated, including several by-products. Under high temperatures with a various metal transitions and halogen by FeCl 3-I 2 and Cu(NO 3) 2 .3H 2 O and ZnCl 2 catalyst, four compounds were identified employing spectroscopic methods in the reaction product: 7-hydroxy-dehydroabietic acid (5), 1,7-dihydroxy-dehydroabietic acid (6), 7-isopropyl-1-methylphenanthren-9-ol (7) and polymer (8). This modified pine rosin was mainly used as an emulsifier for the synthetic rubber industry, varnish, ink, paper sizing, etc. The products are determined based on LC-MS/MS, UV-Vis, and ATR-FTIR spectroscopy.

Full text

Jurnal Kimia Valensi, Vol 8(1), May 2022, 92-105
Available online at Website: http://journal.uinjkt.ac.id/index.php/valensi
Copyright©2022, Published by Jurnal Kimia Valensi
P-ISSN: 2460-6065, E-ISSN: 2548-3013
Directed Study of Abietic Acid Reaction in Pine Rosin under Non-Precious-
Metal Catalyst
Siti Nurul Afifah, Masruri Masruri*, Arie Srihardyastutie and Moh. Farid Rahman
Chemistry Departement, Faculty of Mathematics and Natural Science, Brawijaya University, Veteran St, 65145
Malang, 65145, Indonesia
*Corresponding author: masruri@ub.ac.id
Received: October 2021; Revision: December 2021; Accepted: April 2022; Available online: May 2022
Abstract
Pine rosin of Pinus merkusii Jung at de Vriese is produced industrially from a distillation process of pine sap.
The high total Indonesian production leads the primary derivatization strategy into several derivates to fulfill the
market demand. Abietic acid (AA) is a major compound in pine rosin, used as the object of observation in this
study. The general methodology for transformation reported involves using palladium (Pd) and platinum (Pt)-
based catalysts. Both are precious metal catalysts to proceed with oxidative dehydrogenative-aromatization of
the rosin. The synthesized product provides dehydroabietic acid (DHA) derivatives in high yield. This paper
reports that non-precious metal-based catalysts such as iron (Fe), zinc (Zn), or copper (Cu) with iodine (I2) were
applied to deliver the reaction by steam cracking without nitrogen (N2) and oxygen (O2) for economical,
efficient, and greenway’s catalyst. It was found that a similar product was isolated, including several by-
products. Under high temperatures with a various metal transitions and halogen by FeCl3-I2 and Cu(NO3)2.3H2O
and ZnCl2 catalyst, four compounds were identified employing spectroscopic methods in the reaction product: 7-
hydroxy-dehydroabietic acid (5), 1,7-dihydroxy-dehydroabietic acid (6), 7-isopropyl-1-methylphenanthren-9-ol
(7) and polymer (8). This modified pine rosin was mainly used as an emulsifier for the synthetic rubber industry,
varnish, ink, paper sizing, etc. The products are determined based on LC-MS/MS, UV-Vis, and ATR-FTIR
spectroscopy.
Keywords: Abietic acid (AA), dehydrogenative-aromatization, dehydroabietic acid (DHA), oxidative-
dehydrogenation, pine rosin.
DOI: 10.15408/jkv.v8i1.22802
1. INTRODUCTION
Pine forest is one of the natural
resources in Indonesia. Pine resin is commonly
exported from Indonesia, known as the third
largest resin producer in the world (Kugler et
al., 2019). It has been used for reforestation in
East Java, including Malang, Jombang, Kediri,
Pasuruan, Blitar, Probolinggo, Jember,
Trenggalek, Banyuwangi, etc. (Corryanti &
Rahmawati, 2015). Gum oleoresin is pain rosin
of Pinus Merkusii Jung at De Vriese’s tree, and
pine rosin distillation was produced by gum
rosin and tall oil rosin (Kuspradini et al.,
2016), which contains 80-90% abietane
skeletone and 10-20% terpene skeletone (Y. Li
et al., 2019) The compound of abietane
skeletone 80-90% is isomers of rosin acid and
abietic acid (AA) compound is 40-60%
(Brocas et al., 2014). However, abietic acid’s
pure compound was not readily for sale in the
chemical market. Therefore, the scientist of
pine rosin used gum rosin as a starting material
or sample for their experience because the
major compound in the gum rosin is abietic
acid that can occur in the reaction in the pine
rosin.
An abietic acid (AA) with the typical
formula C19H29COOH has two conjugated
double bonds but not good physical and
chemical properties because it is unstable,
resistant to color, easily oxidized, and cheaply
for industry (Frances et al., 2020).
Dehydroabietic acid (DHA) is a high modified
product of abietic acid (AA) from
dehydrogenation reaction by Palladium (Pd) or
Platinum (Pt) (Abdel-raouf & Abdul, 2018)
and a significantly modified product of rosin
acid compound for the anti-microbial agent,

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anti-fungal, anti-cancer, anti-inflammatory, the
ingredient in synthetic rubber, chewing gum,
adhesives, paints, glues, tires, hair removal
wax, detergents, soaps, etc. (Gonçalves & Al.,
2018).
In recent years, the dehydrogenation of
abietic acid’s compound has become exciting
research for the pine rosin industry. However,
the process of modifying pine rosin was
constrained by the high production cost and
environmental pollution effects of the chemical
reaction process (Primaningtyas & Widyorini,
2020). Transition metals have provided
halogens such as Br2, I2, and Cl2 the electrons
they need to fill their d-type vacant orbitals
(Upham et al., 2016) for C-C bonds and C-H
heteroatoms in abietic acid compounds by
oxidative and aromatize dehydrogenation of C-
H bonds (Y. Li et al., 2019). Mostafalu et al.
(2017) reported that the addition of Iodine (I2)
or sulfur (S) in various FeCl3 catalysts had
given the dehydroabietic acid (DHA) product
72% and 51% (Mostafalu et al., 2017). ZnCl2
and FeCl3 are various metal chlorides with
base activators (Setianingsih, 2017). Zn2+ and
Cu2+ are divalent cations, and Fe3+ is trivalent
metal cations by octahedral’s structures
(Hongo, 2008). Bromine is another halogen
compound that can be combined with a non-
precious metal catalyst such as CaCO3 to
support a high yield percentage value in the
modification reaction of abietic acid to
dehydroabietic acid and their derivates
(Alvarez, 2007). As a versatile and
environmentally benign reagent, iodine
compounds in higher oxidation states have
become popular organic chemistry. Recently,
Iodine has been discovered to be a catalytic
agent in numerous oxidative transformations
for new C-O, C-N, C-C, C=C, and C-H bonds
in organic compounds.
These catalytic transformations are often
similar to non-precious metal-catalyzed
reactions, with the advantage of being
environmentally sustainable and efficiently
utilizing natural resources. In current industrial
applications, Iodine is underutilized because it
is relatively cheap and environmental friendly
(Yusubov & Zhdankin, 2015). Nowadays,
oxidative dehydrogenative aromatization has
high energy efficiency because it occurs at a
low exothermic reaction temperature, and the
energy required is not high. Industry can
process reactions at low cost and temperature
because it decreases greenhouse gas emissions
(Lemonidou, 2010). The method of steam
cracking in industrial oxidative
dehydrogenation can decrease economic and
environmental restrictions (Skoufa Z, 2015).
This work aims to investigate the effect of a
non-precious metal-based catalyst such as an
Iron (Fe), Copper (Cu), and Zinc (Zn)
performance for halogen (Iodine or I2) in
oxidative and aromatize dehydrogenation’s
reaction of abietic acid by steam cracking (Gu
& Al., 2020).
Figure 1. Chemical structures of abietic acid
2. MATERIALS AND METHODS
Materials
Abietic acid is a major compound in
Gondorukem’s rosin was commercially
available from PT. Perhutani Anugerah Kimia
(PAK) in Trenggalek, East Java, Indonesia.
The reagents used in this study were pro
analyst (p.a) grade produced by Merck i.e.
NaOH (s), ZnCl2 (s), Cu(NO3)2.3H2O (s), n-
Hexane (aq), TLC plates, hydrochloric acid
(aq), chloroform (aq) and Ferrum chloride (s)
and iodine by SmartLab.
Modification’s Reaction of Abietic acid’s in
Pine’s Rosin by High Temperature
The gondorukem‘s sample is prepared
by mashed with mortar. Ten grams of gum
rosin (contain an abietic acid 60% or 6 gram)
turned into weighed in three neck round
backside flask equipped with a mechanical
stirrer, temperature sensor, and condenser
(Mostafalu et al., 2017). The one pot reaction
became run at 280 0C without N2 atmosphere
to get an oxidation. The first temperature was
found of the rosin started to melt. While the
reaction of temperature was reached, the
FeCl3-I2, Cu-addition and Zn-Addition at
dosages 1 wt% (see Table 1) was added to the
reaction. More samples were taken during for
each hour to monitoring by TLC (Thin Layer
Chromatography) by eluen’s ratio n-

Directed Study of Abietic Acid’s Reaction in Pine’s Rosin Under Non-Precious Metal Catalyst Afifah et. al.
94
hexane:ethyl acetate = 8:2, UV VIS (Ultra
Violet Visible) Spectroscopy and FT-IR
(Fourrier Transform Infra-Red) analysis in a
bottle sample and the reaction was continued
for 6 hours.
Neutralization of Product’s Reaction
After the reaction, 25 mL of ethyl
acetate was added to solubilize the product’s
reaction. Liquid extraction was carried out to
extract a rosin acid compound by adding 12.5
mL NaOH 1.5 M to form a dissolved salt.
Then a dissolved salt was extracted again by
adding 12.5 mL 1.5 HCl 1.5 M to form
organic’s an aqueous’s layer phases. The
organic phase layer will be analyzed as a
synthesized product of dehydroabietic acid’s
derivate. This extraction was repeated three
times. The organic phase was subsequently
separated. After the separation, the organic
phase in ethyl acetate was evaporated using a
rotary evaporator then the product reaction was
analyzed by LCMS/MS (Liquid
Chromatography-Mass
Spectrophotometry/Mass Spectrophotometry).
The functional group of rosin acid was
generated and analyzed from the oxidative
dehydrogenation-aromatization’s reaction of
ATR-FTIR (Attenuated Total Reflection-
Fourier Transform Infra-Red) by the
instrument of SHIMADZU Single Reflection
ATR. Accessory (QATR-S) IR Spirit (Fourier
Transform Infrared Spectrometer) Serial No.
A224158. The UV-VIS spectrophotometer was
used to calculate an abietic acid and the
dehydroabietic acid derivate level by the
following equation:
According to Yongwan Gu (2020), E241,
E250, E273, and E276 can be defined by the
absorption at the wavelength (241 nm, 250 nm,
273 nm, and 276 nm), c for sample
concentration (g/L), l for cuvette thickness
(cm), k for coefficient specific absorption of
pure abietic acid can be equated to 28, f for
coefficient specific absorption of pure
dehydroabietic acid can be equated to 1,06
(Meesupthong et al., 2020) by using
GENESYS 10S UV VIS spectrometer with
dual beam-interface reference and the
maximum absorption of samples was used by
SHIMADZU UV-1601 with UV PROBE’s
software.
Attenuated Total Reflection-Fourier
Transform Infra-Red (ATR-FTIR)
spectroscopy of natural material is needed to
generate of functional group in rosin acid by
giving overlapping spectral bands in a mixture
plot for identifying a material (Martín-ramos,
2018). Smeds et al. (2017) reported that a
High-Performance Liquid Chromatography
(HPLC) Quadrupole Time of Flight Mass
Spectrometry (QTOF-MS/MS) was identified
the molar mass (MM) and fragmentation of
major and minor organic compounds in pine-
sap (Smeds et al., 2017) those abietic acid
(AA), hydroxylated rosin acid (OH-RA),
dehydroabietic acid (DHA)’s derivatives, and
another resin acid (RA). The starting gum rosin
was company available from PT. Perhutani
Anugerah Kimia (PAK) and the product
reactions were analyzed by UPLC-
QTOFMS/MS (Waters) with ACQUITY
UPLC®H-Class System (Waters) equipped
with ACQUITY UPLC®HSS C18 (1.8 µm 2.1
x 150 mm) capillary column, with flow rate 0.2
ml/minutes for 23 minutes. Collision energy is
4 Volt and 25-70 Volt.
The experiment was repeated for other
various catalysts and reagents by FeCl3, I2,
Cu(NO3)2.3H2O, and ZnCl2 in table 1.
Table 1. Experimental design of dehydrogenation-aromatization reaction for 6 h and temperature 280 0C
Variation
Gum
Rosin
FeCl3
Iodine (I2)
Cu(NO3)2.3H2O
ZnCl2
Various 1 (FeCl3-I2)
10 g
0.1 g
0.1 g
0 g
0 g
Various 2 (Cu-add)
10 g
0.1 g
0.1 g
0.1 g
0 g
Various 3 (Zn-add)
10 g
0.1 g
0.1 g
0 g
0.1 g

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3. RESULTS AND DISCUSSION
Effect of Variation Non-Metal Precious on
the Oxidative-Dehydrogenative-
Aromatization’s Product of Reaction
The compound of abietic acid (AA) was
detected in starting material of pine rosin,
which is shown in Fig. 2. Fig. 2 presented the
abietic acid peak in pine of rosin
chromatogram by retention time (12.42 min),
and the isomer compound of abietic acid (iso-
AA) those a levopimaric acid and Neoabietic
acid were presented by retention time (14.28
min). An effect of promoting non-precious-
metal catalyst was given the differences in
product reaction in LCMS/MS chromatogram.
A various of FeCl3-I2 1% (w%) was expressed
product reaction for dehydrogenation and
oxidation 2 step’s reaction was 1,7-dihydroxy
dehydroabietic acid about 33.46% by
retention’s time in 15.17 minutes. The product
of dehydrogenation and oxidation 1 step’s
reaction was 7-hydroxy dehydroabietic acid,
about 20.71% by the time of retention in 12.66
minutes. However, the product’s oxidation 1
step and stepwise dehydrogenation reaction
was 7-isopropyl-1-methylphenantrene-9-ol
only 1.31% at 11.64 minutes.
An effect of promoted Cu-addition in
the various catalyst by FeCl3-I2-
Cu(NO3)2.3H2O 1% (w%) was given some
product’s reaction for dehydrogenation and
oxidation 1 step’s reaction was 7-hydroxy
dehydroabietic acid about 49.15% by
retention’s time in 12.81 minutes.
Nevertheless, the dehydrogenation and
oxidation 2-step reaction product was 1,7-
dihydroxy-dehydroabietic acid, only 2.79% by
the time of retention in 10.02 minutes.
However, the product’s oxidation 1 step and
stepwise dehydrogenation reaction was 7-
isopropyl-1-methylphenantrene-9-ol only
0.76% at 10,81 minutes. The Cu-addition in
the various catalyst of FeCl3-I2-
Cu(NO3)2.3H2O 1% (w%) was given the
polymer’s product at 18.04 minutes, about
17.94%.
An effect of promoted Zn-addition in the
various catalyst by FeCl3-I2-ZnCl2 1% (w%)
was given some product’s reaction for
dehydrogenation and oxidation 1 step’s
reaction was 7-hydroxy dehydroabietic acid
about 43.06% by retention’s time in 12.81
minutes. Nevertheless, the dehydrogenation
and oxidation 2-step reaction product was 1,7-
dihydroxy-dehydroabietic acid, only 4.25% by
the time of retention in 10.02 minutes.
However, the product’s oxidation 1 step and
stepwise dehydrogenation reaction were 7-
isopropyl-1-methylphenantrene-9-ol of about
10,9% at 14.37 minutes. The Zn-addition in
various catalysts of FeCl3-I2- ZnCl2 1% (w%)
was given the polymer’s product at 18.02
minutes, only about 4.99%.
In previous work by this experiment, the
synthesis of intermediate compound of
dehydroabietic acid (DHA) at m/z 300.21 and
their derivatives by various non-precious metal
catalysts has been described in Fig.3. An
abietic acid (AA) at m/z 302.22 has isomerized
with levopimaric acid at m/z 302.22 and
neoabietic acid at m/z 302.22. However, that
compound was not stable and changed an
Abietic Acid (AA) for a better compound.
Abietic acid (AA) has been dehydrogenated to
dehydroabietic acid (DHA) and has been
hydroxylated to 7-hydroxy abietic acid (7-OH-
DHA) at m/z 318.22, then has detilated and
removed an etil to m/z 290,19; had
dehydrogenated to 7-
hydroxydehydrodehydroabietic acid (7-OH-
DHA) at m/z 316.20 and then has etilated to
m/z 288.17 for the time leading from 1 hour to
6 hours reaction (Berg & Boon 2000). The
dehydroabietic acid (DHA) at m/z 300.21 has
transformed to 7-Hydroxydehydroabietic acid
(7-OH-DHA) at m/z 316.20 through
hydroxylation in dehydrogenation and
oxidation 1 step’s reaction. The product’s
reaction of 1,7-dihydroxydehydroabietic acid
(1,7-di-OH-DHA) at m/z 332.20 has been
transformed from dehydrogenation and
oxidation 2-step reaction of abietic acid (AA)
or derived from some compound of 7-hydroxy-
dehydroabietic acid (7-OH-DHA) that oxidized
again after oxidized 1-step. Dehydroabietic
acid (di-DHA) compound at m/z 298.19
derived from the intermediate’s compound of
dehydroabietic acid (DHA) that
dehydrogenized again for 2 step
dehydrogenation. An oxidative
dehydrogenative-aromatization reaction was
identified, which found a phenanthrene’s
derivatives derived from some 7-hydroxy-
dehydroabietic acid’s (7-OH-DHA) compound
at m/z 266.17. Then, this compound was
transformed into the polymer of dehydroabietic
acid (Poly-DHA) because of the high-
temperature reaction at 280 °C. Chlorine (Cl)
is a very efficient halogen promoter, while
Iodine (I2) is the least efficient, but iodine (I2)

Directed Study of Abietic Acid’s Reaction in Pine’s Rosin Under Non-Precious Metal Catalyst Afifah et. al.
96
is the best effective halogen promoter because
of the ease with which HI is oxidized for
oxidative dehydrogenation (Pasternak &
Vadekar, 1970).
The mechanism reaction of oxidative
dehydrogenation’s reaction, aromatization
dehydrogenation’s reaction, and
polymerization’s reaction has been explained
in Figure 4. First, the unstable abietic acid’s
(AA) isomer was, namely neoabietic acid (Iso-
AA) and levopimaric acid (Iso-AA), will
undergo isomerization to form an abietic’s acid
(AA), which was more stable due to the
influence of high temperature. Second,
abietic’s acid (AA) will be dehydrogenated
into an intermediate compound, dehydroabietic
acid (DHA). Third, dehydroabietic acid (DHA)
will be directly oxidized in stage 1 to form 7-
hydroxy dehydroabietic acid (7-OH-DHA),
and this compound will be directly oxidized
again (step 2) to form 1,7-dihydroxy
dehydroabietic acid (1,7-di-OH-DHA). Fourth,
some of the compounds (5) will undergo
dehydrogenation reactions to produce
phenanthrene derivatives (7), and further,
under the influence of high temperature, will
undergo polymerization reactions to form a
polymer product. The selectivity of this
reaction cannot be calculated quantitatively
because the compound of this product was
formed through 1 original abietic acid
compound and isomer of abietic acid, which
directly undergoes various reactions. The level
of the product’s reaction was also determined
by lewis acid present in the non-precious
metal’s transition catalyst. The stronger lewis’s
acid increased the oxidation’s reaction or
product, but the weaker lewis’s acid decreased
the oxidation’s reaction of product.
Figure 2. Total ion LCMS/MS chromatogram the pine rosin with various of non-precious metal’s catalyst and
product’s reaction

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Figure 3. Oxidative-dehydrogenative–aromatization reaction paths of diterpenoid compounds (abietic acid) in
pine of rosin with the relative suggested of oxidative-dehydrogenation and aromatization (Smeds et al., 2017;
Adilbekov, 2016)

Directed Study of Abietic Acid’s Reaction in Pine’s Rosin Under Non-Precious Metal Catalyst Afifah et. al.
98
Figure 4. The mechanism’s process reaction of oxydative-dehydrogenation and aromatization-dehydrogenation
by various catalyst of FeCl3-I2-ZnCl2 / FeCl3-I2-Cu(NO3)2.3H2O / FeCl3-I2 (1%)

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Table 2. ESI-QtoF-LC/MS Fragmentation of Abietic Acid (AA), Dehydroabietic Acid (DHA) and their
derivates
Compound
Molecular
Formula,
[M-H]-
Mono-
Isotopic
Mass, [M-
H]-
MS2 and MS3 Fragmentations, m/z
(Relative Abundance)a
Abietic Acid (AA)
C20H29O2
301.2170
MS2: 299,2011 (100); MS3:297,6426 (100)
Levopimaric Acid (Iso-AA)
C20H29O2
301.2193
MS2: 299,2010 (100); MS3:299,2010 (100)
Neoabietic Acid (Iso-AA)
C20H29O2
301.2193
MS2: 299,2010 (100); MS3:299,2010 (100)
Dehydroabietic Acid (DHA)
C20H27O2
299.2020
MS2: 297,1856 (100); MS3:287,2013 (100)
7-Hydroxyabietic Acid (7-
OH-AA)
C20H29O3
317.2115
MS2: 293,1752 (100); MS3:285,1850 (100)
7-Hydroxy-Dehydroabietic
Acid (7-OH-DHA)
C20H27O3
315.1954
MS2: 269,1896 (100); MS3:187,1118 (100)
1,7-Dihydroxydehydroabietic
Acid (1,7-di-OH-DHA)
C20H27O4
331.1901
MS2: 313,1791(98), 329 (100); MS3:
301,1791 (100)
Didehydroabietic Acid (Di-
DHA)
C20H25O2
297.1850
MS2: 277,1797 (100); MS3: 251,1792 (100)
7-isopropyl-1-
methylphenanthren-9-ol
C19H21O
265.1601
MS2:250,1362(100); MS3:222,1051 (100)
7-Hydroxy-De-RA (7-OH-de-
RA)
C18H23O3
287.1647
MS2:285,1846(100); MS3:159,0805 (100)
7-Hydroxy-RA (7-OH-RA)
C18H25O3
289.1437
MS2:240,1745(100); MS3:212,1434(100)
Polymer
C20H29O2
871.5733
MS2:821,5660(100); MS3:705,4750 (100)
Thirteen resin acid compounds can be
classified by ESI-QtoF-LC/MS investigation
from Table 2. Based on the fragmentation table
of abietic acid (AA), dehydroabietic acid
(DHA) and its derivatives can be seen in the
deprotonated molecular ions ([M-H]-) in MS1,
MS2, and MS3. Abietic acid (AA) and its
isomers of abietic’s acid (neoabietic acid and
levopimaric acid) were detected in m/z 301.
The first product of dehydrogenation is
Dehydroabietic Acid (DHA), which was
detected at m/z 299, and this product of
dehydroabietic acid (DHA) is only
intermediate. This intermediate compound of
dehydroabietic acid would immediately
undergo an oxidation reaction in stage 1 and
stage 2. The oxidation product from abietic
acid (AA) and dehydroabietic acid (DHA) was
detected at m/z 317 for 7-Hydroxyabietic acid
(7-OH-AA) and 315 for 7-Hydroxy-
Dehydroabietic acid (7-OH-DHA). The
reaction of the second dehydrogenation
detected a fragment in m/z 297. The other
product also detected a fragment at m/z 287 for
7-Hydroxy-Dehydro-Rosin Acid (7-OH-De-
RA) and fragment m/z 289 for 7-Hydroxy-
Rosin Acid (7-OH-RA). The compound of 7-
hydroxy-dehydroabietic acid (7-OH-DHA)
was to get an oxidation reaction in step 2 to
form 1,7-dihydroxy-dehydroabietic acid (1,7-
OH-DHA). The ESI-QtoF-LC/MS results can
be investigated that 7-isopropyl-1-
methylphenanthren-9-ol (7) and polymer’s
product of modification an abietic acid (AA)
by the ion m/z 265 (100) and 871 (100). The
abietic acid (AA) and dehydroabietic acid
(DHA) can be continuously extracted and
analyzed by LC/MS without any other
pretreatments because a sample can easily be
analyzed as it is easy to implement simple,
fast, selective, and sensitive (Mitani, 2007).
The compound of abietic acid was
detected in starting material of pine rosin, as
shown in Fig. 5. Fig. 5 presents the abietic acid
peak absorption in wavelength 241 nm until
250 nm by UV VIS spectrometer of
SHIMADZU UV-1601 with UV PROBE’s
software. The pine rosin was weighed at 0,1 gr
by analytical scale in a 10 ml volumetric flask.
The ethyl acetate solvent was added and
homogenized to wholly dissolved. After the
solvent was dissolved, the solution was quickly
qualitatively analyzed by UV VIS
spectrometer of SHIMADZU UV-1601 with
UV PROBE’s software (Li, 2014).
The quantitative analysis of abietic acid
(AA) and dehydroabietic acid (DHA) levels
was represented by Yongwan Gu (2019). An
abietic acid (AA) and dehydroabietic acid
(DHA) levels were calculated by the equation
of (i) in multiwavelength absorption for abietic
acid (AA) in wavelengths of 241 nm and 250

Directed Study of Abietic Acid’s Reaction in Pine’s Rosin Under Non-Precious Metal Catalyst Afifah et. al.
100
nm, then dehydroabietic acid (DHA) in
wavelength of 273 nm and 276 nm. The
content compound of abietic acid (AA) and
dehydroabietic acid (DHA) has reacted with
various catalysts in the non-precious metal
catalyst.
Fig. 6 compares the intercorrelations
among the % content compound, various
catalyzed, and reaction times. A weak positive
correlation was found between % content
compound, various catalyzed, and reaction
time. A correlation was also present between
the optimum time of reaction and % content
compound of dehydroabietic acid (DHA) in
product reaction and excellent variation of
catalyzed in this reaction. Xuan Dai et al.
(2018) explained that non-precious metals (Ni,
Fe, Co, and Cu) are efficient’s catalysts for
oxidative dehydrogenation aromatization
reaction in hydrocarbon compounds using
molecular oxygen as the ultimate oxidant
(Meesupthong et al., 2018). Huahua Fan et al.
(2020) said the presence of Zn and Fe can
increase selectivity and % yield of aromatic
products in ethane oxidative dehydrogenation
by DFT study (Fan. Huahua, 2020). The results
indicated that relatively optimum of reaction
time by promoted a non-precious metal
catalyst in FeCl3-I2 1% (b/b) is 5’th hours,
FeCl3-I2-Cu(NO3)2.3H2O 1% (b/b) is only 2
hours, and for various catalysts of FeCl3-I2-
ZnCl2 1% (b/b) is 4 hours. The effect of
various catalysts in the oxidative
dehydrogenation and aromatization of abietic
acid (AA) to dehydroabietic acid’s (DHA)
derivatives were investigated in Fig. 6.
Figure 5. UV spectra of abietic acid in starting material of pine rosin. The scan range of the UV spectra
Figure 6. The quantitave analysis of abietic acid’s (1) content to dehydroabietic acid’s derivatives (2) content
by variuos catalyst with FeCl3-I2 1% (w%) (A), FeCl3-I2-Cu(NO3)2.3H2O 1% (w%) (B), and FeCl3-I2-ZnCl2 1%
(w%) (C) for 6 hours

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101
Table 3. Main band observed on FTIR spectra of reaction resin with variuos catalyst under inverstigation and
their assignment based on the literature data of table 1 (in supplementary’s data)
Bond No.
Pine of Rosin
Various 1 (FeCl3-I2)
Various 2 (Cu-add)
Various 3 (Zn-add)
1
3424.33
3293.12 sh
3441.45
3437.17 s
2
3077.76 w
3060.65 sh
Nd
3063.50 vw
3
2938.00
2957.96 s
2928.01 s
2956.54 s
2926.59 s
2957.96 s
2928.01 s
4
2870.96
2868.11 w
2866.69
2868.11
6
-
1741.40 vw
1798.45
1741.40
9
1697.19 s
1694.34 w
1652.98
1688.63
10
nd
1600.21 w
1601.64
1601.64
11
nd
1496.10
-
1496.10
12
1463.29
1459.01 w
1456.16
1457.59
*nd is not detection, vw is very weak, s is strong, and sh is shoulder, Various 1 (FeCl3-I2 (1%)), Various 2 (FeCl3-I2-Cu Add
(1%)), and Various 3 (FeCl3-I2-Zn Add (1%)).
Table 4. FT-IR band positions and intensities prior to normalization of the C=C and =C-H exocylic methylene
groups, alkene (phenolic resin), benzene (aromatic’s ring) and hydroxil region of the spectra, and their relevant
assignment (Pagacz, 2019)
Band/cm-1
Sample and Intensity
Assignment
Pine of
Rosin
FeCl3-I2
(1%)
FeCl3-I2-Cu
Add (1%)
FeCl3-I2-Zn
Add (1%)
1630–1650 cm-1
17.48
47.64
59.60
44.90
C=C (exocyclic
methylene groups,
typical of Resins)
1590-1615 cm-1
-
54.02
56.94
50.14
C=C aromatic ring
1490-1515 cm-1
50.74
62.33
45.51
66.59
C=C typical of phenolic
resins
2845-2865 cm-1
22.09
23.42
31.72
23.01
Sym. Stretc. =CH2
3000-3100 cm-1
36.63
55.36
12.63
63.85
=C-H aromatic ring
3230-3550 cm-1
39.60
66.61
25.85
45.26
-O-H hydroxil
Table 5. FT-IR band positions and intensities after normalization of the C=C and =C-H exocylic methylene
groups, alkene (phenolic resin), benzene (aromatic’s ring) and hydroxil region of the spectra, and their relevant
assignment (Pagacz, 2019)
Band/cm-1
Sample and Intensity
Assignment
Pine of
Rosin
FeCl3-I2
(1%)
FeCl3-I2-Cu
Add (1%)
FeCl3-I2-Zn
Add (1%)
1630–1650 cm-1
0
0.62246
1
0.50229
C=C (exocyclic
methylene groups,
typical of resins)
1590-1615 cm-1
0
0.78643
0.94337
0.62253
C=C aromatic ring
1490-1515 cm-1
1
1
0.70002
1
C=C typical of phenolic
resins
2845-2865 cm-1
0.1386
0
0.40643
0
sym. stretc. =CH2
3000-3100 cm-1
0.57577
0.82087
0
0.93713
=C-H aromatic ring
3230-3550 cm-1
0.66506
1
0.28146
0.51056
-O-H hydroxil
The ATR-FTIR spectra of Pine rosin
and three product reaction with various non-
precious metal catalysts are shown in TABLE
3. Their bands have been correlated with those
of other rosin acids (RA) reported in the
literature (see TABLE 1 in supplementary’s
data). Band assignments are summarized in
TABLE 1. Then the analysis of Peak Intensity

Directed Study of Abietic Acid’s Reaction in Pine’s Rosin Under Non-Precious Metal Catalyst Afifah et. al.
102
and FT-IR band position before normalization
are shown in TABLE 4. After normalizing the
intensity of several peaks, it can be seen that
the dominant chemical reaction occurred from
the chemical group functional to be identified
by the high value in TABLE 5. The intensity of
a band 1490-1515 cm-1 matching the C=C
vibration of phenolic resin groups is high, then
the dominant vibration of OH (Hydroxyl) in
band 3230-3550 cm-1 for the dominant’s
reaction of dehydrogenation and oxidation 1-2
step’s reaction, the next a vibration of C=C
typical aromatic ring for a band 1590-1615 cm-
1 and the last vibration is C=C of exocyclic
methylene groups for a band 1630-1650 cm-1
for all the reaction of dehydrogenation’s
reaction. Another interesting observation is a
band about 3000-3100 cm-1 related to =C-H
aromatic ring vibration, and the last is
symmetry stretching of =CH2 vibration in a
band 2845-2865 cm-1 for the non-dominant
dehydrogenation and aromatization reaction
(Pagacz, 2019). The dominant vibration is
C=C phenolic resin, aromatic’s ring, =C-H
aromatic’s ring is higher these experiments are
dehydrogenation and aromatization reaction
(Ramos, Martin. Fernandez, 2018).
Fig. 7 shows spectra of pine rosin as
starting material and their’s product reaction
by non-precious metal catalysts promoted with
FeCl3-I2 1%; FeCl3-I2-Cu(NO3)2.3H2O 1%,
and FeCl3-I2-ZnCl2. Changing the C=C and
=C-H functional group and -OH functional
group can be identified by FT-IR
spectrophotometry. The hydroxyl group (-OH)
vibration is usually the most intense signal on
the FT-IR spectra. The complex compound of
gum rosin and its modification product by high
thermal can be noticeable by the side of the
FT-IR spectra, mainly in the hydroxyl area. In
order to succeed in the signals in the hydroxyl
area (3230-3550 cm-1), we follow a correct
approach. This reaction of modification of
abietic acid (AA) can be distinguished from
three types of vibration, the first is due to
(C=C) vibrations, the second is related to =C-
H vibration, and the last –O-H (hydroxyl)
vibration. One more unique band from all
peaks is a strong C=C of phenolic resin at
1490-1515 cm-1, the other is a C=C aromatic
ring at 1590-1615 cm-1, the other between the
weak vibration is C=C exocyclic methylene
groups. Another vibration is =C-H alkene is
less visible than =C-H aromatic’s ring
vibration and the stretching vibration of
hydroxyl (-O-H) on the spectra of FT-IR (Y,
2014). It indicates that pine of rosin was
dehydrogenated, oxidized, and aromatized well
in gum rosin’s modified product.
Figure 7. FTIR spectra of pine of rosin and three samples with various non-precious metal’s catalyst

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103
4. CONCLUSION
In this study, we examine the
effectiveness of variation non-precious metal
catalysts (as Fe, Cu, and Zn) and halogen (I2 –
Iodine) as an oxidant for modification’s
reaction in pine rosin. This research used an
ESI-Quadrupole Time of Flight-Liquid
Chromatography-Mass Spectrometry (QtoF-
LC/MS) and successfully obtained thirteen
derived rosin acid (RA) compounds to
investigate a chemical reaction with various
non-precious-metal catalysts (Fe, Cu, Zn) and
halogen oxidant (I2) in high temperature. The
product reactions were derivated from the
intermediate compound of dehydroabietic acid
(DHA) that 7-hydroxyabietic acid (7-OH-AA);
7-hydroxydehydroabietic acid (7-OH-DHA);
1,7-dihydroxydehydroabietic acid (1,7-Di-OH-
DHA); dehydroabietic acid (Di-DHA); 7-
hydroxy-dehydro-rosin acid (7-OH-De-RA); 7-
hydroxy-rosin acid (7-OH-RA); 7-Isopropyl-1-
methylphenantrene-9-ol; and polymer’s
product. Nevertheless, the object’s compounds
of product reaction in this study were only
four, 7-hydroxy-dehydroabietic acid (7-OH-
DHA), 1,7-dihydroxydehydroabietic acid (1,7-
di-OH-DHA), 7-Isopropyl-1-
methylphenantrene-9-ol, and polymer’s
compound. The qualitative UV spectra suggest
that abietic acid (AA) has a similar absorption
peak from 241 nm to 250 nm and the
dehydroabietic acid (DHA) in 273 nm to 276
nm. It was chosen as the wavelength test for
quantitative analysis by multiwavelength. The
ATR-FTIR method was proper to identify the
chemical reaction process of pine rosin based
on a set of band positions. The vibrational
functional group between C=C of phenolic
resin, aromatic ring, and exocyclic methylene
group; =C-H of aromatic’s ring and alkene,
and –OH hydroxyl’s vibration is clearly
explained the chemical reaction of oxidative
dehydrogenation and aromatization of an
abietic acid (AA) to form derivatives of
dehydroabietic acid (DHA) as an
intermediate’s product.
ACKNOWLEDGMENTS
We are grateful because this research is
supported financially by Hibah Penelitian
Unggulan (HPU) Perguruan Tinggi (2021)
from Brawijaya’s University. Higher
Education of Indonesia. The authors gratefully
acknowledge the contributions of Mr. Widji
Sulistjo and Mr. Hadi Kurniawan.
REFERENCES
Abdel-raouf, M. E., and M.Abdul, M. (2018).
Rosin : Chemistry, Derivatives, and
Applications : A Review. Bio-Accent,
4(039), 1–16.
Adilbekov, D. (2016). ANALYTICAL ANALYSIS
OF ROMAN AMPHORAE. October.
Alvarez, M. et al. (2007). Regioselective Routes
Towards 14-Hydroxyabietane Diterpenes.
A Formal Synthesis of Immunosuppressant
(-)-Triptolide from (+)-Abietic Acid.
Tetrahedron, 63(45), 11204–11212.
https://doi.org/10.1016/j.tet.2007.07.088
Berg, K.J., Boon J.J. (2000). Mass Spectrometric
Methodology for the Analysis of Highly
Oxidized Diterpenoid Acids in Old Master
Paintings. Journal of Mass Spectrometry,
35(512–533).
Brocas, A., Llevlot, A., and Mantzaridis, C. (2014).
Epoxidized Rosin Acids As Co-Precursors
For Epoxy Resins. Design Monomers and
Polymers, 17(4), 301–310.
https://doi.org/10.1080/15685551.2013.84
0504
Corryanti., and Rahmawati, R. (2015). Terobosan
Memperbanyak Pinus (Pinus Merkusii).
PUSLITBANG PERUM PERHUTANI.
Fan. Huahua. (2020). Mechanistic Understanding
of Ethane Dehydrogenation and
Aromatization over Zn/ZSM-5: Effects of
Zn Midification and CO2 Co-Reactant.
https://doi.org/10.1039/D0CY01566K
Frances, M., Gardere, Y., and Duret, E. (2020).
Effect of Heat Treatment on Pinus Pinaster
Rosin: A study of Physico Chemical
Changes and Influence on the Quality of
Rosin Linseed Oil Varnish. Industrial
Crops and Products, 155(July).
https://doi.org/10.1016/j.indcrop.2020.112
789
Gonçalves, M. D., and Al., E. (2018).
Dehydroabietic Acid Isolated from Pinus
Elliottii Exerts in Vitro Antileishmanial
Action by Pro-Oxidant Effect, Inducing
ROS Production in Promastigote and
Downregulating Nrf2/Ferritin Expression
in Amastigote Forms of Leishmania
Amazonensis. Fitoterapia, 128, 224–232.
https://doi.org/10.1016/J.FITOTE.2018.05.
027

Directed Study of Abietic Acid’s Reaction in Pine’s Rosin Under Non-Precious Metal Catalyst Afifah et. al.
104
Gu, Y., and Al., E. (2020). Effects of Pretreated
Carbon Supports in Pd/C Catalysts on
Rosin Disproportionation Catalytic
Performance. Chemical Engineering
Science, 216(February), 115588.
https://doi.org/10.1016/j.ces.2020.115588
Hongo, T. (2008). Adsorption Ability for Several
Harmful Anions and Thermal Behaviour of
Zn-Fe Layered Double Hydroxide. 116,
1350, 192–197.
Kugler, S., Ossowicz, P., Kornelia, M., and
Wierzbicka, E. (2019). Advances in Rosin-
Based Chemicals: The Latest Recipes,
Applications and Future Trends.
Molecules, 24(9), 1–51.
https://doi.org/10.3390/molecules2409165
1
Kuspradini, H., Rosamah, E., Sukaton, E., Arung,
E. T., and Kusuma, I. W. (2016).
Pengenalan Jenis Getah : Gum Lateks
Resin.
Lemonidou, H. E. (2010). AA. Ni–Nb–O Mixed
Oxides as Highly Active and Selective
Catalysts for Ethane Production Via
Ethane Oxidative Dehydrogenation.
Journal Catalyst, 270, 67–75.
Li, J. L. X. L. W. (2014). Kinetics of Gum Rosin
Oxidation Under 365 nm Ultraviolet
Irradiation. Monatsh Chem, 209–212.
https://doi.org/10.1007/s00706-013-1014-7
Li, Y. et al. (2019). Iodine-Promoted Intermolecular
Dehydrogenation Diamination : Synthesis
of Unsymmetrical α, β-diamido Ketones.
An Asian Journal.
https://doi.org/10.1002/asia.201900170
Li, Y., Xu, X., Niu, M., and Chen, J. (2019).
Thermal Stability of Abietic Acid and Its
Oxidation Products. Energy and Fuels,
33(11), 11200–11209.
https://doi.org/10.1021/acs.energyfuels.9b
02855
Martín-ramos, P. et al. (2018). Potential of ATR-
FTIR Spectroscopy for the Classification
of Natural Resins. BEMS Reports, 4(1), 3–
6.
Meesupthong, R., Yingkamhaeng, N., Nimchua, T.,
Pinmanee, P., Mussatto, S. I., Li, B., and
Sukyai, P. (2020). Xylanase pretreatment
of energy cane enables facile cellulose
nanocrystal isolation. Cellulose.
https://doi.org/10.1007/s10570-020-03559-
y
Meesupthong, R., Yinkamhaenf, N., and Al., E.
(2018). Aromatization of Hydrocarbons by
Oxidative Dehydrogenation Catalyzed by
Nickel Porphyrin with Molecular Oxygen.
Catalysis Communications, 117, 85–89.
https://doi.org/https://doi.org/10.1016/j.cat
com.2018.09.003
Mitani, K. et al. (2007). Analysis of Abietic Acid
and Dehydroabietic Acid in Food Samples
by In-Tube Solid-Phase Microextraction
Coupled with Liquid Chromatography-
Mass Spectrometry. Journal of
Chromatography A, 1146(1), 61–66.
https://doi.org/10.1016/j.chroma.2007.01.1
18
Mostafalu, R., Heydari, A., Banaci, A., and
Ghorbani, F. (2017). The Use of Palladium
Nanoparticles Supported on Active Carbon
for Synthesis of Disproportionate Rosin (
DPR ). Journal of Nanostructure in
Chemistry, 7(1), 61–66.
https://doi.org/10.1007/s40097-017-0220-y
Pagacz, J. et al. (2019). Preliminary Thermal
Characterization of Natural Resins from
Different Botanical Sources and
Geological Environments. Journal of
Thermal Analysis and Calorimetry, 0.
https://doi.org/10.1007/s10973-019-08157-
0
Pasternak, I.S., Vadekar, M. (1970). Sulphur /
Halogen Promoted Oxidative
Dehydrogenation of Hydrocarbons. The
Canadian Journal of Chemical
Engineering, 48.
Primaningtyas, A., and Widyorini, R. (2020).
Evaluasi Proses Produksi Industri
Gondorukem dari Tinjauan Aliran Massa
dan Energi (Studi kasus PGT Sapuran)
[Evaluation of the Gum Rosin Industrial
Production Process Based on Mass and
Energy Balances (PGT Sapuran case
study). Jurnal Riset Industri Hasil Hutan,
12(1), 39.
https://doi.org/10.24111/jrihh.v12i1.5996
Ramos, Martin. Fernandez, P. (2018). Potential of
ATR-FTIR spectroscopy for the
classification of Natural Resins. BEMS
Rep., 4(1), 3–6.
Setianingsih, T. (2017). Metal Precious.
International Journal of ChemTech
Research, 10(6), 10–19.

Jurnal Kimia Valensi, Vol. 8, No. 1, May 2022 [92-105] P-ISSN : 2460-6065, E-ISSN : 2548-3013
105
Skoufa Z, et al. (2015). On Ethane ODH
Mechanism and Nature of Active Sites
Over NiO-Based Catalysts Via Isotopic
Labeling and Methanol Sorption Studies.
J. Catalyst, 322, 118–129.
Smeds, A. I., Eklund, P. C., and M. Willfor, S.
(2017). Characterization of High-Molar-
Mass Fractions in a Scots Pine (Pinus
Sylvestris L.) Knotwood Ethanol Extract.
DE GRUYER.
Upham, D. C., Gordon, M. J., Metin, H., and
McFariand, E. W. (2016). Halogen-
Mediated Oxidative Dehydrogenation of
Propane Using Iodine or Molten Lithium
Iodide. Catalysis Letters.
https://doi.org/10.1007/s10562-016-1701-1
Y., T. (2014). Analysis of The Components of Hard
Resin in Hops (Humulus Lupulus L.) and
Structural Elucidation of Their
Transformation Products Formed During
the Brewing process. Journal of
Agricultural and Food Chemistry, 62(47),
11602–11612.
Yusubov, M. S., and Zhdankin, V. V. (2015).
Iodine Catalysis : A green Alternative to
Transition Metals in Organic Chemistry
and Technology. Resource-Efficient
Technologies, 782, 1–19.
https://doi.org/10.1016/j.reffit.2015.06.001