Journal of the UniversityS.

ofNenkova,
ChemicalT. Technology
Radoykova,and
K. Stanulov
Metallurgy, 46, 2, 2011, 109-120

PREPARATION AND ANTIOXIDANT PROPERTIES

OF BIOMASS LOW MOLECULAR PHENOLIC COMPOUNDS
(REVIEW)
S. Nenkova, T. Radoykova, K. Stanulov

University of Chemical Technology and Metallurgy Received 05 April 2011

8 Kl. Ohridski, 1756 Sofia, Bulgaria Accepted 12 May 2011
E-mail: nusha_v@mail.bg

ABSTRACT

Modern chemical industry is based on natural energy sources - coal, petroleum and natural gas, which have been
formed by decomposition of vegetable materials in the course of millions of years. As their reserves are limited and
gradually exhausted, one of the main tasks of the industry is to provide the complete, versatile and most effective
utilization of the raw materials.
The chemical treatment of wood to cellulose and monosaccharides is connected with the conversion of c.a. one
third of its mass into a lignin component as a residue. The bioethanol production from raw materials increases and hence
the lignin utilization starts to attract significant interest. Because of its chemical structure peculiarities it is a potential
source of valuable products of possible application in many different areas. In this aspect the lignin, which is in fact a waste
product in the process of vegetable materials treatment, is a suitable source of monomer phenolic compounds of well
known inhibiting effect towards hydrocarbons oxidation.
Keywords: lignin, low-molecular phenolic compounds, antioxidant activity.

INTRODUCTION The interaction of lignin with aqueous solutions

Lignin is widely spread, renewable, amorphous
natural polymer, containing phenylpropane units (Fig. 1).
The latter are derivatives of syringol, guaiacol and p-
hydroxyphenol. They are interconnected through ether-
and C-C bonds [1] forming thus a very complex three-
dimensional polymer matrix [2]. They are in fact the source
of low-molecular phenolic compounds (LMPC) [3-7].
METHODS FOR LIGNIN DESTRUCTION
Lignin is the biomass component of most diffi-
cult destruction because of its complex structure, in-
solubility and high molecular mass.
of sodium hydroxide is the main reaction proceeding in
the course of plant tissues delignification and the alka-
line methods [8] used for fibrous materials production.
Furthermore, lignin alkaline treatment is widely applied
in residual hydrolyzed lignin activation aiming its utili-
zation. It is found that lignin hydrolysis under alkaline
conditions proceeds with a tendency to destruction [9].
The destruction of lignin [10, 11] and its model com-
pounds [12] is carried out in absence of a catalyst at
temperature values close to the critical one (400oC and
350oC) and pressure of 25 ÌPa. The aim is to facilitate
lignin’s full conversion to phenolic compounds which
are important raw materials for production of antioxi-
dants, dyes, drugs, etc. [10].

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 Journal of the University of Chemical Technology and Metallurgy, 46, 2, 2011
Fig. 1. Schematic structural formula of a lignin’s fragment.
The alkaline hydrolysis of lignin results in its
depolymerization through the rupture of ether- and de-
struction C − C bonds connecting the phenylpropane
units. The method leads to the production of low-mo-
lecular monomer phenols (2,6-dimethoxyphenol
(syringol); 3,6-dimethoxy-4-hydroxy acetophenone; 4-
ethylguaiacol; 2-methoxyphenol (guaiacol); 4-ethyl-2-
methoxyphenol; 2–methoxy–4-propylphenol; 4-
methylcatehole; phenol; 4-hydroxy-3,5di-methoxyben-
zaldehyde (syringaldehyde) and 4-hydroxy-3-methoxy-
benzaldehyde (vanillin) [13-17 ], whose separation and
chromatographic identification [7] is comparatively easy.
R.W. Throng et al. carry out lignin destruction
for 1 h at 300oC in a reactor, containing aqueous solu-
tion of NaOH in nitric acid medium [18,19]. The ef-
fect of water and the water-ethanol mixture of 1:1 [20]
as a solvent is studied. It is found that the binary solvent
increases the degree of lignin’s destruction as well as
the amount of phenols soluble in ether, but decreases
the selectivity towards production of syringol, guaiacol
and phenol when compared to that achieved in water
only. The phenols yield is followed in dependence of
NaOH concentration in the range from 1 to 6 %mass. A
higher value is obtained in case of solutions of concen-
tration of 1-2 %mass. The yield of the individual phenols
is also optimal in this concentration range. At a higher
NaOH concentration the guaiacol yield decreases es-
sentially, which shows that guaiacol demethoxylation is
fast under these conditions.
110
Miller, J.F. studies also the destruction of lignin
and its model compounds in alcohol solutions of bases
[21]. A high degree of conversion is achieved in case of
lignin treatment for 10-15 min in a mixture of
KOH / EtOH at 290oC. Analogous experiments with
NaOH , CsOH , LiOH , Ca (OH )2 are carried out.
They show that the strong bases favor a higher degree of
conversion.
Enkvist [22] finds out that catechol and its alkyl
derivatives are obtained in case of black lye heating at
310oC in presence of NaOH in N 2 atmosphere. The
hydroxide used is in a concentration of 18 % in respect
to the dry compound in the initial raw material. A study
on a model compound of lignin shows that the alkaline
agent facilitates the rupture of the ether- and the C − C
bonds leading to volatile phenols. The author concludes
that the presence of water of at least 10 % in respect to
dry lignin is required to ensure sodium hydroxide ac-
tivity in the thermolysis course.
Domburg et al. [23] investigate the effect of al-
kaline additives like NaOH , K 2CO3, and Na2CO3
on lignin’s thermal reactivity, the phenols composition
and the yield of pyrolytic oils. It is found that the pres-
ence of 5 % aqueous solution of NaOH leads to the
highest yield of guaiacol and syringol without increas-
ing the amount of secondary pyrolytic phenols like phe-
nol, cresols and catechols.
The experiments on alkaline destruction of lig-
nin samples in presence of anthraquinone and Rh as a
catalyst show that the yield of monomer phenols like
guaiacol, syringol and similar aldehydes is increased
when compared to that obtained in a catalyst absence
[24]. These experiments verify the catalytic activity of
Rh and other transient metals in the process of prepa-
ration of guaiacol and its derivatives. It is also found
that facilitates the formation of keto-derivatives. Cata-
lysts like Co(III) and Mn(III) are used for the oxida-
tive destruction of lignin’s model compounds to phenols
[25]. Lignin decomposition in an aqueous-alkaline medium
in presence of anthraquinone [26] and of lignin model com-
pounds in presence of anthrahydroquinone [27] is studied
as well. The results obtained show that the shorter reaction
time results in formation of alkenephenols like eugenol and
related products, while the longer reaction time favors the
increase of the yield of simple phenols like guaiacol.
Oxygen-containing compounds are obtained in
the course of a catalytic hydrothermal treatment of wood
 S. Nenkova, T. Radoykova, K. Stanulov
biomass using Rb and Cs carbonates for 15 min at
280oC [28]. The results are compared to those obtained
in case of an alkaline solution absence. Solvents like
ether, ethylacetate and acetone are used for extraction
and are subsequently regenerated through evaporation.
The liquid and solid products are separated under
vacuum. The liquid phase is extracted with diethylether
and then with ethylacetate, while the solid phase is ex-
tracted with acetone in Soxlet extraction apparatus. The
composition of the extracts obtained is analyzed by GC-
MS. It is found that the presence of Rb and Cs carbon-
ates increases the extracts yield when compared to those
obtained in a catalyst absence. The GC-MS analysis
shows that phenol compounds are the main products
found in the ether extract obtained both in a catalyst
and a non-catalyst treatment. The amount of 2-
methoxyphenol is higher in case of RbCO3 presence when
compared to that obtained when CsCO3 is used. Ke-
tones are the main compounds found in the ethylacetate
extract, while the Sokslet extract contains phenols, ke-
tones and furan derivatives. It is evident that the appli-
cation of alkaline catalysts hinders charcoal formation
and subsequently increases the yield of liquid products
of wood’s hydrothermal treatment. The authors conclude
that the wood preliminary impregnation with an aque-
ous alkaline solution and the stirring in the course of
the treatment affect greatly the yield of oil products.
The methods used for the production of mono-
mer phenols through thermochemical conversion of
biomass are reviewed [29]. It is shown that the prepara-
tion of phenolic compounds like 2-methoxyphenol, 2,6-
dimethoxyphenol and their alkyl derivatives depends on
the experimental conditions used. The small dimensions
of the wood particles, the short reactor time, the re-
duced pressure and moderate pyrolysis temperature fa-
vor these products formation. The dehydrogenation of
the OH -groups in the alkyl chain of the lignin
phenylpropane structural unit is the main chemical re-
action in biomass conversion to phenols. This reaction
is followed by bonds rupture. The β − O − 4 -aryl-ether
bonds are among those which are most frequently af-
fected. The usage of solvents which are hydrogen do-
nors like tetralin and/or hydrogen atmosphere in ther-
mal decomposition of biomass limits the improvement
of phenols yield. The regeneration of tetralin as well as
naphthalene formation resulting from hydrogen-donor
reactions and reactor pressure increase hinder their
commercial application. Organic catalysts like an-
thraquinone, salts and oxides of Cu ( II ) and Fe ( III )
are used to obtain some guaiacol and syringol com-
pounds containing aldehyde groups. Vanillin, one of the
compounds which are usually produced from lignin, is
obtained through alkaline oxidation of lignin. It is evi-
dent that pyrolysis of wood impregnated by inorganic
alkaline catalysts like NaOH brings about higher yields
of individual phenols. The type of NaOH addition as
well as the pyrolysis conditions differ in the studies con-
sidered.
The products of autohydrolysis (hydrothermal
treatment) of rice husks and corncobs are analyzed.
The process is carried out at 205oC in presence of wa-
ter at a hydromodule of 1:8 (liquid: solid phase). Van-
illin, syringol, syringaldehyde, guaiacol, 4-vinylguai-
acol, 4-vinylphenol are among the lignin products ob-
tained [30]. Furfural is a product of the corresponding
chemicelluloses [30].
The hydrolysis treatment of wood in presence of
an acidic catalyst (dilute solution of sulphuric acid) and
temperature of 180oC leads to the polysaccharides tran-
sition to the solution, while the lignin remains in a solid
state (technical hydrolyzed lignin - THL). THL differs
from the natural and the other types of lignin materials.
The acidic and the hydrolyzing effect of the catalyst
changes the original three-dimensional lignin structure.
It becomes more complicated and dense which in turn
leads to low reactivity and solubility in alkaline and neu-
tral solvents [31]. One of the well accepted methods for
THL activation is connected with its alkaline treatment
under different conditions [32]. The authors find that
the treatment with 5.0 % NaOH leads to the produc-
tion of lignin products of highest hydrophilicity and the
best porosity. In the course of this process a significant
part of the lignin passes to the solution and thus a dis-
persed system, containing products of the destruction
and some other changes that had affected the lignin com-
plex, is obtained. The alkaline solution can be acidified
and high-molecular products of complex structure, called
lignin acids, are obtained. Chudakov [33] assumes that
the ether- and some of the C − C bonds are ruptured
because of the joint effect of the highly hydrolyzing agent
(the alkaline solution) and the thermal destruction. This
results in preparation of alkaline-activated lignin of
higher solubility, of higher content of acidic (including
phenolic) OH groups which determines the potentially
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 Journal of the University of Chemical Technology and Metallurgy, 46, 2, 2011
higher reactivity of the lignin product. Low-molecular
products of unknown nature remain in the solution
[33, 34].
The detailed investigation of the alkaline hydroly-
sis of lignin carried out by S. Nenkova [34] shows that
the optimal conditions required for lignin’s transition to
the solution are as follows: temperature of 180oC, 5 %
NaOH , hydromodule of 1:10 and treatment duration
of 6 hours. This type of treatment leads to the most
intensified lignin dissolution which is connected with
the strongest destruction. The products obtained do not
precipitate in the alkaline solution. It is verified that
the alkali-activated hydrolyzed lignin (AAHL) produced
is free from the residual polysaccharides, has a lower
molecular mass, higher reactivity and can be used for
the production of azodyes [35], for wood modification
[36], etc.
S. Nenkova et al. study the alkaline hydrolysis of
THL and other vegetable biomasses (poplar wood and
Fig. 2. Principal scheme of the process of low-molecular phenolic compounds production.
112
poplar bark) under conditions which are favorable for
waste lignin activation (temperature of 180oC, duration
of 2, 4 and 6 h , 3, 5 and 7 % aqueous solution of
NaOH , lignin/aqueous solution of NaOH ratio
(hydromodule) of 1:6, 1:8 and 1:10). The aim is to in-
vestigate the nature and the possible application of the
low-molecular products which are left in the liquid
phase after higher-molecular fraction precipitation [4-
6, 37]. The principal scheme of the process of produc-
tion of low-molecular phenolic compounds (LMPC)
from lignin is shown in Fig. 2.
The liquid fraction containing the non-precipi-
tated lignin is subjected to triple extraction with tolu-
ene. The organic/aqueous phase ratio is 1:5. The latter
has been initially determined as the optimal one [5].
The choice of a non-polar solvent for the extraction
aims at limitation of the amount of side more-polar
products (ketones, aldehydes, acids) whose anti-oxidant
properties are low. The extracts obtained are analyzed
 S. Nenkova, T. Radoykova, K. Stanulov
by GC-MS. The composition of the hydrolysis low-
molecular products which are found in the liquid phase
after extraction with toluene and the possibility of prepar-
ing LMPC through solid-liquid extraction of AAHL (in
Soxhlet apparatus for 24 hours with diethyl ether) are
studied. The liquid phase separated after the extraction
with toluene (poplar bark wood, 180oC, 4 hours, 5 %
NaOH , hydromodule of 1:8) is subjected to double
extraction with ethylacetate at an organic-liquid phase
ratio of 1:5. The solvent has been selected on the ground
of data collected in the course of an analogous extrac-
tion [28]. The extracts obtained after eliminating the
solvent through vacuum-evaporation are analyzed by FT-
IR. It is found that different aromatic carbonyl com-
pounds are present in both extracts (it is assumed that
most of the carbonyl groups are incorporated in aro-
matic acids, while the other are included in aromatic
esters or ketones). These compounds can be used in
other investigations of practical importance. It is found
that the shorter duration of the alkaline treatment of
THL results not only in lower yield of LMPC but also
in a difference of the extracts composition [5]. In case
of duration of 2 and 4 hours the main products are as
follows: 3-hydroxy-4-methoxybenzaldehyde (vanillin) of
a yield of 51.41 % (it presents 45.08 % of the LMPC
obtained) and 1-(4-hydroxy-3-methoxyphenyl) ethanone
of a yield of 26.14 % (it presents 29.04 % of the LMPC
obtained). This is most probably due to the fact that the
short time of treatment does not provide destruction to
methoxyhenols. At 6 hours-treatment the main product is
2-methoxyphenol with a yield of 56.80 %. The investiga-
tion is carried out with THL produced from coniferous
wood and this is why the monomer phenols contain
only one methoxy group.
The studies on the alkaline hydrolysis of a vegetable
biomass of different kind (THL, wood and bark) show
that the response to the change in the experimental con-
ditions is identical. The increase both of the duration
and of NaOH concentration leads to an increase of
the LMPC yield [5, 6]. This is due to a great extent to
the destruction of the lignin macromolecule. The in-
crease of the hydromodule from 1:6 to 1:8 results in an
increase of the solubility of THL with about 10 %. The
further ratio increase to 1:10 has practically no further
effect on THL solubility and the yield of the precipi-
tated activated lignin. Although the amount of hydro-
lyzed products stays unchanged, the increase of the
hydromodule brings about an increase of the LMPC
yield [5]. It is experimentally verified that the best con-
ditions for THL treatment aiming AAHL preparation
refer to the application of 5 %-solution of NaOH and
duration of 6 hours. It is found as well that the increase
of NaOH solution concentration to 7 % in case of hy-
drolysis duration of up to 6 hours does not affect the
LMPC yield, but a hydromodule not lower than 1:8 is
recommended to ensure an adequate liquid reaction
medium [6]. The monomer phenols obtained contain
two methoxy groups because the predominating lignin
in the deciduous wood treated has syring units.
The amount of the products of hydrolysis of poplar
wood, polar bark and THL is comparatively considered
[4]. It is found that the greater part of the wood’s lignin
is dissolved and the yield of LMPC is higher in case of
wood’s hydrolysis although the lignin amount in bark is
much greater. This is most probably due to the fact
that anthraquinone has been added as a catalyst in case
of wood’s hydrolysis. It not only facilitates the lignin
destruction and the rupture of fragments as LMPC but
prevents the polysaccharides destruction. It is to be noted
that the bark lignin is more condensed. The lowest yield
of LMPC is obtained in case of THL hydrolysis for 6
hours. This is most probably due to the more condensed
structure of THL. This is verified by the results obtained
in the course of wood and bark hydrolysis. Greater
amounts of monomer phenols like phenol, 4-ethyl-2-
methoxyphenol (and some other unidentified phenol
compounds detected in the chromatogram) are obtained.
Table 1 shows the composition of LMPC mixtures ob-
tained in the course of 6 hours of alkaline hydrolysis of
THL, poplar bark and poplar wood sawdust [4, 6].
NATURAL METHOXY PHENOLS AS
ANTIOXIDANTS
Petroleum products as well as those from the
petrochemical processing are unstable in the presence
of oxygen and decompose through auto-oxidation [38].
It is proved that the liquid phase oxidation of hydrocar-
bons goes through a chain-radical mechanism with chain
development and ramification [39, 40]. The antioxidants
used for fuel chemical stability improvement are prod-
ucts of hydrocarbons radical-chain oxidation. Phenols
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 Journal of the University of Chemical Technology and Metallurgy, 46, 2, 2011

Table 1. Identified monomer compounds.

Poplar wood bark, THL, 6h,
Sawdust of poplar wood,
6h, 7 % NaOH, 5 %NaOH,
6h, 5% NaOH, h.m.-1:8
Compound h.m.-1:10 h.m.-1:8
Retention Area, Area, Area,
time, min % % %
Phenol 2.91 3.21 2.58 2.01
* 3.51 3.64 3.63 2.59
2-methoxyphenol 3.81 23.11 15.86 56.80
* 3.88 - 1.95 -
* 4.24 - 1.39 -
* 4.28 4.23 4.51 1.43
4-ethyl-2-methoxyphenol 5.46 1.03 3.17 -
2,6-dimethoxyphenol 6.07 38.04 29.38 6.68
3-hydroxy-4-
methoxybenzaldehyde 6.55 3.01 6.67 18.48
(vanilline)
1-[4-hydroxy-
7.27 8.74 10.52 10.96
3-methoxyphenyl] ethanone
* 7.53 4.18 6.71 1.05
4-hydroxy-3,5-
dimethoxybenzaldehyde 8.78 0.76 3.95 -
( syringaldehyde)
1-[4-hydroxy-3,5-
dimethoxyphenyl] ethanone
9.50 10.05 10.04 -

* Unidentified compounds.

substituted by tertiary alkyl groups (i.e. ionol -2,6-di-
tert-butyl-4-methylphenol) are the most widely used in
practice. They react very fast with peroxide radicals and
thus they stop the chain reaction proceeding. The phe-
noxy radicals obtained interacts with hydroperoxide
forming stable quinone structures (cyclohexadiene per-
oxide, Fig. 3) [41].
The phenol antioxidation properties depend on
the substituents number and nature. In general, the in-
hibitor activity depends on the rate of cleavage of a func-
tional group hydrogen atom. The activity increases with
the ease in which the cleavage reaction proceeds. The
alkylphenols inhibiting effect is determined by the sub-
Fig. 3. Interaction of phenols with peroxide radicals.
stituents polarity and the steric factor (the dimension
and configuration of the substituents in o-position). In
general, the inhibitors effectiveness increases with the
substituent’s polarity decrease and the increase of the
steric factor. There is a correlation between the effec-
tiveness and the alkylphenols redox potential. The lat-
ter decrease results in an increase of these compounds
antioxidant action [41, 42].
The antioxidation effect of the methoxyphenols
produced in lignin alkaline treatment is tested by study-
ing the oxygen absorption of liquid paraffin in a labora-
tory manometric installation [43]. It is shown that their
action is comparable to that of the most widely used
low temperature oxidation inhibitor – ionol. The FT-
IR spectral investigations prove the effectiveness of the
isolated phenolic compounds.
The antioxidation effect of methoxyphenols pro-
duced in the poplar bark alkaline treatment is tested by
determining the gasoline induction period (at a quan-
tity of 25, 75 and 200 ppm) of the phenolic compounds
[44]. It is verified that the latter are a mixture of 2-
methoxyphenol, 2,6-dimethoxyphenol, 3-hydroxy-4-
methoxybenzaldehyde and 1-(4-hydroxy-3-methoxy-
phenyl) ethanone. Comparative tests are performed with

114
 S. Nenkova, T. Radoykova, K. Stanulov
ionol (25 ppm). Commercial gasoline A95 is used in
this investigation. Because of its high induction period
dicumyl peroxide is added (0.1g /100 ml gasoline) as an
oxidation initiator. It is found that the induction period
increases with the increase of methoxyphenols concen-
tration (Fig. 4). The highest inhibition effect thus ob-
served is at a methoxyphenols concentration of 200 ppm.
It is confirmed by IR spectra. It is important to add
that the spectra of samples containing methoxyphenols
and ionol of a concentration of 25 ppm are identical.
The antioxidant properties of phenolic com-
pounds obtained from wood are well studied. The bark
of various tree species is widely used in traditional folk
and Tibetan medicine for its anti-inflammatory and
analgesic properties. It has been verified that this effect
is due to the presence of biologically active compounds
which can be easily extracted [45]. It has been estab-
lished that the phenolic compounds present in the bark
are in fact flavonoids, tannins and phenylcarboxylic ac-
ids which are antioxidants of strong anti-inflammatory,
analgesic and antibacterial properties [45-47].
The antioxidant activity of phenols depends on
the substituents number and nature [48, 49]. It is found
that the presence of electron-donor and large groups at
ortho and para positions hinders the oxidation processes.
The antioxidant effect decreases in the line: 4-alyl-2,6-
dimethoxyphenol ≥ p,p’-biphenol > eugenol > 2-alyl-
6-methylphenol > honikiol > magnolol > caffeine acid
> p-ethylphenol > guaiacol [50].
The antioxidant activity of the native phenolic
compounds is characterized with the application of a
free radical method using 1,1-diphenyl-2-pierylhydrazyl
Fig. 4. Kinetic curves of gasoline oxidation.
(DPPH). The activity of the latter is lower than that of
•
oxygen-containing free radicals like OH , RO • , ROO
•
−
and O2 , but the authors suggest this procedure for evalu-
ating the radical acceptance activity of lignin and re-
lated substances [51-54]. It is found that the antioxi-
dant properties of the latter decrease essentially with
the introduction of a carbonyl group in the side chain
[50, 54]. This can be illustrated by the change in the
values of anti-radical power (ARP) of the lignin model
compounds in the following line: propylguaicol >
guaiacylpropnol-1 > guaiacol >> guaiacylpropanone-1;
coniferyl alcohol >> coniferylaldehyde [52]. The pres-
ence of a double bond in the side propane chain de-
creases the acceptance ability of isoguaiacol when com-
pared to that of guaiacol and propylguaiacol. At the
same time the presence of a double bond between C β
and Cγ atoms in the side chain of eugenol increases
this ability. This is in correspondence with the ARP
values of 1.94 and 3.7, found with the application of the
DPPH method by Brand-Williams et al. [53].The same
tendency is outlined when considering the values of the
power constants of eugenol and isoeugenol reactions
with oxidants like the radicals N3·, OH·, and particu-
larly CCl3O2· [55].
The antioxidant activity of the product of beech
wood tar distillation is verified. It is found that the
main components are as follows: 2-methoxyphenol, 2-
methoxy-4-methylphenol, 3-methylphenol, 4- methyl-
phenol, 2- methylphenol and phenol [56, 57].
Fats oxidation can be prevented or inhibited by
adding synthetic antioxidants like 2-tert-butyl-4-
methoxyphenol, 2,6-di-tert- butyl-4-methylphenol
(ionol). The interest towards naturally derived antioxi-
dants is increasing. It is found that the extract obtained
from the herb taheebo containing mainly phenolic com-
pounds has a well pronounced antioxidant effect. In fact
the GC-MS analysis carried out shows the presence of
4-methoxybenzaldehyde, 4-ethoxyphenol, 4-methoxy-
benzylalcohol [58].
It is assumed that the antioxidant effect of the
preserving smoke is due to the prevention of lipid
peroxidation through chain-radical reactions breaking.
It is established that methoxyphenols are the compounds
of essential importance for the smoke preserving and
antioxidant effect [59-62]. The antioxidant activity of
the smoke obtained in the course of incineration of wood
of different kind under different conditions is investi-
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 Journal of the University of Chemical Technology and Metallurgy, 46, 2, 2011
gated [63-65]. It is found that 2,6-dimethoxyphenols
with 4-alkenyl and 4-alkyl groups have the strongest
antioxidant activity. These compounds present 60-70 %
of the total dimethoxyphenols amount in the gas evolved
in the course of deciduous wood incineration [66]. The
difference in the composition of the smoke obtained in
coniferous and deciduous wood incineration is due to
the lignin’s different structure. The alkyl-, alkenyl- and
carbonyl-containing groups of phenols obtained in wood
incineration are in fact residues of the initial C 3 chain
of the lignin. It is assumed that the antioxidant proper-
ties of these compounds are due to phenols oxidation
to phenoxy radicals of lower activity [67]. The methyl
(alkyl) and the methoxide (alkoxide) groups at ortho
and para position stabilize the phenoxy radicals which
results further in increase of the antioxidant properties.
The stabilizing effect of the methoxy group is greater
than this of the methyl group which is in correspon-
dence with the redox potentials values of phenols con-
taining these substituents [67, 68].
The gas obtained in the course of birch wood
incineration is composed mainly of syringyl compounds
(Sy-3,5-dimethoxy-4-hydroxyphenyl compounds). It is
verified that the conjugated double bonds of
SyCH = CH 2 and SyCH = CHCH 3 stabilize the phe-
noxy radical which results in higher antioxidant activity
of these dominating components of the gas. The evident
difference between GuCH = CHCH 3 and
GuCH 2CH = CH 2 which has a non-conjugated
double bond is well illustrated [54, 55]. The conjugated
bond effect corresponds approximately to the size of
the additional methoxy group in SyCH 2CH = CH 2
(when compared to GuCH 2 CH = CH 2 , Gu − 3 -
methoxy-4-hydroxyphenyl compounds) [54].
It is expected that phenols with CH 2 side group
( SyCH 3 , SyCH 2CH 3 , SyCH 2CH = CH 2 ) will
have similar activities, besides higher than that of SyH
[50, 54]. It is verified that the electron-accepting á-car-
bonyl group of SyCHO and SyCOCH 3 destabilizes
the phenoxy radical which in turn leads to lower anti-
oxidant activity [54, 68], while the carbonyl group of
SyCH = CHCHO compensates the conjugated
double bond [69]. It is concluded [64] that the 2,6-
dimethoxyphenols can counteract more effectively the
cell lipid peroxidation than antioxidants of similar re-
dox potentials but with no large groups at ortho posi-
tion [70]. SyCH 2CH = CH 2 is determined as the most
116
effective free radicals acceptor among the gas com-
pounds evolved [64].
The correlation between the redox potential values
and the radical acceptance ability is revealed in ref. [71],
while Rosenwald concludes that every effective phenol has
a redox potential value lower than 0.7 V [72]. These inves-
tigations do not treat the substituents effect on phenols
activity. But the dependence of the radical eliminating ac-
tivity on the redox potential of ortho-methoxy substituted
lignin compounds is investigated [52, 67]. It is found that
the compounds with two methoxy groups have higher an-
tioxidant activity which is in correspondence with the data
on redox potential values decrease from 0,87 V to 0, 68 V
for radicals of 4-methylphenol and 2-methoxy-4-
methylphenol, respectively [67,73].
The effectiveness as antioxidants in medical and
diet products of lignin and some related to it monomer
and dimer compounds contained in the wood lye is also
investigated [54, 74-77].
The antioxidant activity of phenolic compounds
prepared by hydrothermal treatment of olive tree is stud-
ied. Syringol and syringaldehyde are the most abundant
volatile phenolic compounds found there. Guaiacol, van-
illin and other methoxyphenols are also identified [78].
Ortho-methoxyphenols like eugenol (2-methoxy-
4-(prop-2-enyl) phenol), isoeugenol (2-methoxy-4-(Å)-
prop-1-enyl) phenol) are components of different spices
widely used in food industry. These compounds present
definite interest because of their anti-inflammatory
and chemo-therapeutical properties resulting from their
antioxidant activity [79, 80]. It is reported that vanillin
(3-methoxy-4-hydroxybenzaldehyde) has chemo-thera-
peutical effect in a carcinogen test [81].
CONCLUSIONS
The possibilities for preparation of valuable prod-
ucts of antioxidant properties using vegetable biomass
are reviewed. The utilization of lignin, the main waste
product of chemically treated wood is thoroughly con-
sidered. The numerous studies on the methods of lig-
nin destruction to low-molecular phenolic compounds
and the utilization of the latter as antioxidants are con-
sidered. The inhibiting effect of these compounds pre-
sents a definite fundamental interest. Its application in
motor fuels stabilization, in food industry and medi-
cine is of practical important as well.
 S. Nenkova, T. Radoykova, K. Stanulov
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