Synthesis and antiradical activity of hybrid antioxidants based on isobornylphenols

Article abstract of DOI:10.1134/S1070363216100133

Alkylation of isobornylphenols with allylbenzene in the presence of homogeneous and heterogeneous catalysts of different nature has been studied. The maximum yield of phenols containing isobornyl and 1-phenylpropyl moieties has been achieved in the presen

Full text of DOI:10.1134/S1070363216100133

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 10, pp. 2325–2331. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © I.Yu. Chukicheva, О.V. Sukrusheva, L.I. Mazaletskaya, А.V. Kuchin, 2016, published in Zhurnal Obshchei Khimii, 2016, Vol. 86,
No. 10, pp. 1678–1684.
Synthesis and Antiradical Activity
of Hybrid Antioxidants Based on Isobornylphenols
I. Yu. Chukichevaa, О. V. Sukrushevaa*, L. I. Mazaletskayab, and А. V. Kuchina
a Institute of Chemistry, Komi Scientific Center, Ural Branch, Russian Academy of Sciences,
ul. Pervomaiskaya 48, Syktyvkar, 167982 Russia
*e-mail: Sukrusheva@mail.ru
b N.M. Emanuel Institute of Biochemical Physics of Russian Academy of Sciences, Moscow, Russia
Received March 14, 2016
Abstract—Alkylation of isobornylphenols with allylbenzene in the presence of homogeneous and hetero-
geneous catalysts of different nature has been studied. The maximum yield of phenols containing isobornyl and
1-phenylpropyl moieties has been achieved in the presence of catalyst FIBAN K-1 at 100°С and catalyst
concentration of 10%. The inhibiting action of isobornylphenol derivatives has been studied in the model
reaction of ethylbenzene oxidation. Hybrid antioxidants on the basis of isobornylphenols were found to actively
interact with peroxide radicals and, therefore, they can be considered as promising additives for conservation of
quality and increase in service life of different organic compounds and materials.
Keywords: isobornylphenols, alkylation, phenyl(alkyl)isobornylphenols, hybrid antioxidants, antiradical activity
DOI: 10.1134/S1070363216100133
Nowadays, sterically hindered phenols are widely
used in polymer industry [1–4]. Thus, antioxidants of
phenol type cover more than 50% of the world market
of stabilizers for plastics and about 30% for resins and
caoutchoucs [5]. Substituted phenols inhibit free-
radical oxidation of organic substrates and improve
working characteristics of articles. Effectiveness of
alkylphenols strongly depends on the size and the
position of the substituents in the aromatic ring [6].
Besides, the advantage of this class of compounds is a
low toxicity as well as a good solubility in hydro-
carbons and practical insolubility in water.
antioxidant BHT, but do not exceed antioxidant
activity of trolox (water-soluble analog of tocopherol).
In the present work, alkylation of racemic 2-iso-
bornyl-4-methylphenol 1 and 2-isobornylphenol 1а
with allylbenzene was studied using homogeneous
[(СH3С6Н4O)3Al, TsOH·H2O, АlCl3] and hetero-
geneous (FIBAN K-1, Amberlyst 15, Amberlyst 36,
Amberlyst 36 Dry and KSF) catalysts. The antiradical
activity of the synthesized compounds was assessed.
Of practical interest for the synthesis of difficultly
accessible o-substituted alkylphenols is the use of
aluminum phenolate as the catalyst. Earlier we have
shown that alkylation of phenol with camphene in the
presence of aluminum phenolate occurs with high
regioselectivity and good yield of о-isobornylphenols
(87%) [9]. Unfortunately, in the reaction studied here
this catalyst was ineffective (Table 1). When using the
Lewis acid catalyst AlCl3 the starting phenol is
dealkylated. In the presence of TsOH·H2O at 100–160°С
the reaction does not take place either, while the
increase in the temperature of the reaction mixture to
180°С promotes isomerization of the terpene moiety of
the starting isobornylphenol and the yield of product 2
is small (30%) (Scheme 1).
A promising direction in improving the properties
of antioxidants is elaboration of polyfunctional
stabilizers or hybrid structures on the basis of phenols.
Introduction in the structure of phenols of bulky
substituents of different nature may lead to a change of
physico-chemical properties.
Earlier, we have synthesized the hybrid phenols
containing in one molecule a bulky isobornyl and tert-
butyl or 1-phenylethyl fragments [7, 8]. The estimation
of the antioxidant activity of isobornylphenols with tert-
butyl substituents showed that the hybrid compounds
have higher antioxidant activity than the liposoluble
2325

2326
CHUKICHEVA et al.
Scheme 1.
8
9
18
OH
R1
OH
7
OH
R1
OH 10
12
R1
1
2
3
6
19
*
cat
5
13
11
16
17
25
4
+
+
+
14
15
21
22
20
R
R
24
23
3
4
2, 2а
1, 1а
R = Me (1, 2), Н (1а, 2а), R1 =
(3, 4).
Heterogeneous catalysts have such advantages over
the homogeneous ones as the easy separation from the
reaction mixture and the possibility of multiple reuse.
excess of allylbenzene does not increase the con-
version of the starting phenols. Performing the reaction
at the ratio phenol : allylbenzene = 2 : 1 did not allow
to increase the yield of the target product either. In this
case, dealkylation of phenol 1 to cresol with
subsequent alkylation of p-cresol with allylbenzene
occurred; 10% of p-cresol and 21% of 2-phenylpropyl-
4-methylphenol was obtained.
KSF clay is a solid Lewis acid containing sulfonic
groups SO3H+ on the surface. This catalyst was shown
to be effective in the synthesis of phenols containing
the isobornyl and tert-butyl substituents in one
molecule [8]. However, alkylation of phenol 1 with
allylbenzene in the presence of KSF does not occur,
either.
Alkylation of phenol 1а gives regioisomers 2а and
3, as well as the disubstituted product 4. Note that in
the presence of sulfocationic catalysts FIBAN K-1 and
Amberlyst 15, 36 and 36 Dry, the p-alkylated phenol 3
is formed in high yield. The largest yield (44%) of
product 3 was achieved in the presence of catalyst
FIBAN K-1 with equimolar ratio of the reagents.
Using the excess of allylbenzene increases the yield of
the products of dialkylation.
FIBAN K-1 is a polypropylene fiber with grafted
copolymer of styrene and divinylbenzene, containing
sulfonic groups SO3H+, and it is an effective catalyst
for the synthesis of methyl-tert-alkyl ethers [10]. The
use of FIBAN K-1 in the studied reaction leads to the
formation of products of alkylation 2, 2a, 3, and 4 with
moderate conversion of the starting phenols 1 and 1а.
The effect of the catalyst concentration, the ratio of the
reagents, and the temperature of the reaction mixture
was studied. It was found that the increase in the
catalyst amount from 5 to 10% caused the increase in
the conversion of the starting phenol and the yield of
the target product. The increase in the temperature to
140°С increases the rate of the reaction, but the
conversion and the yield vary only slightly because of
the processes of dealkylation of the starting isobornyl-
phenol and isomerization of the terpene fragment. In
the reaction of 2-isobornyl-4-methylphenol 1 with
allylbenzene the maximum yield of product 2 (63–
66%) was achieved at the temperature of 100°C and
the amount of the catalyst of 10%. Variation of the
molar ratio of the reagents (1 : 1 or 1 : 2) does not
affect the yield of product 2. Note that the use of
Polystyrene Amberlyst sulfonic acid resins effectively
catalyze hydration and etherification of olefins, de-
hydration of alcohols, and alkylation of phenols [11,
12]. The amount of Amberlyst catalyst (10%) was
chosen according to the literature data [13].
In the presence of macroporous cationites Amberlyst
15, Amberlyst 36, and Amberlyst 36 Dry the reactions
of phenols 1 and 1a proceed with incomplete
conversion (42–68%); besides, the products with the
isomerized terpene fragment are formed. Products 2,
2a, 3, and 4 are formed in the presence of all studied
Amberlyst catalysts practically in equal amounts
irrespective of the temperature of the reaction mixture
and the ratio of the reagents. Therefore, it is impossible
to choose the most effective catalyst.
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SYNTHESIS AND ANTIRADICAL ACTIVITY OF HYBRID ANTIOXIDANTS
Table 1. Alkylation of isobornylphenols with allylbenzene
2327
Composition of the products of
alkylation, %
Phenol:
allylbenzene
Time, Conversion,
Phenol
Catalyst
T, °С
h
%
2
–
2а
–
3
–
4
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
1
(СH3С6Н4O)3Al (10 wt %)
TsOH·H2O (26 mol %)
AlCl3 (10 wt %)
1 : 1
1 : 1
1 : 1
1 : 1
1 : 1
1 : 2
1 : 1
1 : 2
2:1
160
180
100
100
100
100
140
140
140
100
100
140
100
100
100
140
140
100
140
100
140
140
100
100
100
100
140
140
15
3
–
78
100
–
30
–
–
–
0.5
–
–
KSF (100 wt %)
7
10
10
3
–
–
–
FIBAN K-1 (5 wt %)
58
56
66
62
100а
72
72
73
68
66
42
56
54
60
56
100
72
75
74
80
54
66
54
62
57
60
53
55
35
66
63
60
52
55
54
52
50
54
52
–
–
–
–
–
–
–
3
–
–
3
–
–
FIBAN K-1 (10 wt %)
1 : 1
1 : 2
1 : 1
1 : 1
1 : 2
1 : 1
1 : 1
1 : 2
1 : 1
1 : 2
1 : 1
1 : 1
1 : 2
1 : 1
1 : 2
1 : 1
1 : 2
1 : 1
1 : 2
10
10
3
–
–
–
–
–
–
Amberlyst 15 (10 wt %)
Amberlyst 36 10 wt %
6
–
–
6
–
–
6
–
–
6
–
–
6
–
–
Amberlyst 36 Dry (10 wt %)
6
–
–
6
–
–
1а
AlCl3 (10 wt %)
0.5
–
–
FIBAN K-1 (5 wt %)
3
3
6
6
3
–
19
16
19
15
16
15
12
14
38
33
44
35
35
40
40
36
21
25
17
28
19
24
9
–
FIBAN K-1 (10 wt %)
Amberlyst 15 (10 wt %)
Amberlyst 36 (10 wt %)
–
–
–
–
6
6
–
–
17
a Conversion calculated to allylbenzene.
The structure of the products was proved by NMR
Since the starting isobornylphenols 1 and 1a are
1
spectroscopy. In the H and 13C NMR spectra of
racemates, and in the course of the reaction an
additional chiral center at C17 is formed, the products
of alkylation 2, 2a, and 3 are present as mixtures of
diastereomers in the ratio ~1 : 1. Unfortunately, we
phenols 2, 2a, and 3, apart from the signals of terpeno-
phenol moiety, the signals of phenylpropyl substituent
are present.
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2328
CHUKICHEVA et al.
τ, min
τ, min
c0×105, mol/L
Fig. 1. Kinetic curves of oxygen absorption in the initiated
oxidation of ethylbenzene in the (1) absence and (2–4) in
the presence of antioxidant 2 in different concentrations
(mol/L): (2) 3×10–5, (3) 6×10–5, (4) 7.6×10–5. T = 333 K,
wi = 5×10–8 mol L–1 s–1.
Fig. 2. Dependence of the induction period in the initiated
oxidation of ethylbenzene on the initial concentration of
additives: (1) 2a, 6; (2) 7; (3) 3; (4) 2, 5. T = 333 K, wi =
5×10–8 mol L–1 s–1.
failed to isolate individual diastereomers by column
chromatography or crystallization.
induction period (τ) was determined using the
procedure described in [14], and the initial rates of
oxidation. From the slope of the linear dependence of τ
on c0 (Fig. 2) the stoichiometric inhibition coefficient
(f) was calculated by Eq. (1).
We have assessed the antiradical activity of phenols
2, 2a, 3 with respect to the earlier synthesized com-
pounds 5–7 [7], containing the 1-phenylethyl fragment
(Scheme 2).
f = τwi/c0,
(1)
We used the model reaction of initiated oxidation
of ethylbenzene, in which free radicals propagating the
oxidation chains are generated with a constant rate. As
an example, in Fig. 1 the kinetic curves of the
absorption of oxygen in the presence of antioxidant 2
are shown. As can be seen, the oxygen absorption rate
notably decreases in the presence of 2, and a clearly
expressed induction period (τ) is observed, whose
value increases with the initial concentration c0 (Fig. 2).
Similar data were obtained for all studied samples.
where wi denotes the rate of initiation. It can be seen
from Table 2 that the values of f for isobornylphenols
are close to 2. This is in good accordance with the
mechanism of action of phenolic antioxidants,
according to which one molecule of phenol causes the
decay of two free radicals.
To calculate the rate constants of the reaction of
antioxidants with peroxide radicals the values of the
initial rates of oxidation were represented in the
coordinates of Eq. (2) [15]:
From the kinetic curves of the oxygen absorption in
the presence of isobornylphenols 2–3 and 5–7 the
w0/w − w/w0 = fk7c0/k60.5wi0.5
,
(2)
Scheme 2.
OH
OH
OH
5
6
7
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 10 2016

SYNTHESIS AND ANTIRADICAL ACTIVITY OF HYBRID ANTIOXIDANTS
2329
Table 2. Stoichiometric inhibition coefficients (f) and rate
constants of the reaction of antioxidants with peroxide radicals
of ethylbenzene (k7)
where w0 and w are the rates of oxidation in the
absence and in the presence of the additives, respect-
tively, k6 is the rate constant for quadratic recom-
bination of peroxide radicals (k6 = 1.9×107 mol L–1 s–1
[16]). From the slope of straight lines in Fig. 3,
parameter fk7 was calculated (Table 2).
Compound
2
2a
3
5
6
7
fk7×10–4,
20.0
6.6 15.3 17.4 5.2
1.6
L mol–1 s–1
As evident from the data of Table 2, the studied
compounds are active antioxidants, their k7 constant
being dependent on the number, nature and location of
the substituents with respect to the OH group of the
phenol. Constant k7 increases with the number of alkyl
substituents and with the phenylpropyl substituent in
place of the phenylethyl group. For dialkyl-substituted
phenols, introduction of the bulky phenylpropyl
substituent to the p-position to the OH group in 3, as
compared to the о-substituted analog 2а results in two-
fold increase in k7 constant. The k7 constant is known
to sharply decrease with the introduction of two bulky
(for example, tert-butyl) substituents in the o-position
of the phenol molecule. This occurs because bulky
substituents create steric hindrances to the reaction of
phenol with peroxide radicals [17].
f
2.15
9.3
1.9
3.5
2.1 2.15 1.9
7.1 8.1 2.7
2.0
8.0
k7×10–4,
L mol–1 s–1
gistered on a Bruker Avance II 300 spectrometer with
working frequencies 300.17 and 75.48 MHz from
CDCl3 solutions. Chemical shifts are given relative to
the signals of the solvent, the signals were assigned
using 13С JMOD spectra.
The reactions were monitored by TLC on Sorbfil
plates (eluent cyclohexane–Et2O, 50 : 1). The plates
were developed by treatment with the solution of 15 g
КMnO4, 300 mL Н2О, and 0.5 mL of conc. Н2SO4.
The products were separated by column chromato-
graphy on silica Alfa Aesar (70/230μ).
Therefore, we have shown that the maximum yield
of product 2 (63–66%) can be achieved in the presence
of FIBAN K-1 catalyst in concentration of 10%. In
alkylation of 2-isobornylphenol in the presence of
sulfocationic catalysts FIBAN K-1 and Amberlyst, the
p-alkylated phenol 3 is formed in high yield. The
obtained hybrid antioxidants, along with low toxicity
and good solubility in hydrocarbons, actively react
with peroxide radicals and can be considered as
promising additives for preservation of quality and
increase in the durability of various organic com-
pounds and materials.
The inhibiting activity of the hybrid compounds
was studied by volumetric method in the model reac-
tion of oxidation of ethylbenzene initiated by azo-
bisisobutyronitrile. The kinetics of oxygen absorption
during oxidation was registered by the use of highly
sensitive volumetric device at 333 K and the rate of
initiation wi = 5×10–8 mol L–1 s–1. Ethylbenzene with
the dissolved initiator was preliminarily maintained at
EXPERIMENTAL
Catalysts Amberlyst 15 (Fluka), Amberlyst 36
(Aldrich) and Amberlyst 36 Dry were crushed and
calcined at 120°C for 1 h. Montmorillonite KSF (Acros
Organics) with the content of 8–12% of free H2SO4,
АlCl3, and TsOH·H2O were used without preliminary
treatment. FIBAN K-1 catalyst was provided by our
colleagues from Institute of Physical Organic Chemistry
of the Belarus National Academy of Sciences.
c0×105, mol/L
IR spectra were recorded on a Shimadzu IR
Prestige 21 spectrometer in KBr. Melting points were
determined on a Sanyo Gallenkamp MDP350 unit and
Fig. 3. Dependence of the initial rate of inhibited oxidation
of ethylbenzene on the initial concentration of additives in
the coordinates of Eq. (2): (1) 6, (2) 2а, (3) 3, (4) 7, (5) 5,
(6) 2. T = 333 K, wi = 5×10–8 mol L–1 s–1.
1
are uncorrected. Н and 13С NMR spectra were re-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 10 2016

2330
CHUKICHEVA et al.
a desired temperature, then the additive of antioxidant
was introduced, and the kinetics of oxygen absorption
was registered.
12.05 and 12.24 (С10), 12.66 and 12.73 (С9), 20.23 and
20.34 (С8), 21.33 and 21.47 (С18), 27.58 (С5), 28.07
(С19), 34.03 and 34.08 (С3), 39.90 and 39.98 (С6),
45.60 and 45.66 (С17), 46.88 (С2), 47.18 (С4), 48.09
and 48.13 (С7), 49.69 and 49.79 (С1), 119.68 (С15),
125.15 and 125.54 (С14), 126.04 (С16), 126.54 (С23),
128.02 and 128.15 (С22,24), 128.65 and 128.70 (С21,25),
130.18 and 130.22 (С13), 130.35 (С11), 144.03 and
144.09 (С20), 152.93 (С12).
Alkylation of isobornylphenols with allylbenzene.
Two-necked flask equipped with a condenser and a
thermometer was charged with the calculated amounts
of 2-isobornyl-4-methyl-phenol or 2-isobornylphenol
and allylbenzene. Homogeneous [TsOH·H2O, (TolO)3Al,
АlCl3] and heterogeneous sulfocationic catalysts
(FIBAN K-1, Amberlyst 15, Amberlyst 36, Amberlyst
36 Dry and KSF) were used. The reagents and the
catalyst were charged simultaneously. Reaction condi-
tions are given in Table 1. The reaction mixture was
separated by column chromatography (Silica gel
70/230 µ, gradient elution with cyclohexane-Et2O with
increasing fraction of the latter).
4-(1-Phenylpropan-2-yl)-2-(1,7,7-trimethylbi-
cyclo[2.2.1]hept-exo-2-yl)phenol (3). Light-brown oil.
IR spectrum, ν, cm–1: 3535 (ОН), 2953, 2929, 2876,
1
1604, 1501, 1454, 1381, 702. Н NMR spectrum, δ,
10
9
ppm: 0.82 and 0.83 s (3Н, СН3 ), 0.90 s (3Н, СН3 ),
8
0.92 s (3Н, СН3 ), 0.94–0.98 m (3Н, J = 7.5 Hz,
18
СН3 ), 1.41–1.55 m (2Н, Н5,6), 1.64–1.75 m (2Н,
4-Methyl-2-(1-phenylpropan-2-yl)-6-(1,7,7-tri-
methylbicyclo[2.2.1]hept- exo-2-yl)phenol (2). Color-
less powder with mp 95–98°С. IR spectrum, ν, cm–1:
3522, 2953, 2924, 1454, 1458 (CH2, СН3), 1600
Н3,6), 1.90–1.99 m (2Н, Н4,5), 2.08–2.12 m (2Н, Н19),
2.14–2.29 m (1Н, Н3), 3.17 t (1Н, J = 8.7 Hz, Н2),
3.79 t (1Н, J = 7.8 Hz, Н17), 4.81 s (1Н, ОН), 6.71 d
(1Н, J = 8.1 Hz, H14), 6.92–6.97 m (1Н, H13), 7.24–7.33
m (6Н, Н16,21–25). 13С NMR spectrum, δ, ppm: 12.48
and 12.51 (С10), 12.80 and 12.84 (С9), 20.17 and 20.21
(С8), 21.51 (С18), 27.59 (С5), 28.67 (С19), 34.13 and
34.18 (С3), 40.12 and 40.16 (С6), 45.57 and 45.67
(С17), 48.02 (С7), 49.77 (С1), 52.69 and 52.82 (С2,4),
114.82 and 114.85 (С13), 125.83 (С14,16), 127.88 and
128.03 (С22–24), 128.30 (С21,25), 129.32 and 129.34
(С11), 136.57 and 136.73 (С15), 145.78 (С20), 152.84 (С12).
1
(С=С), 864 (C-HAr). Н NMR spectrum, δ, ppm: 0.59
10
18
and 0.77 s (3Н, СН3 ), 0.84 and 0.86 s (3Н, СН3 ),
8
9
0.90 and 0.92 s (3Н, СН3 ), 0.97 s (3Н, СН3 ), 1.35–
1.39 m (2Н, Н5, Н6), 1.52–1.66 m (2Н, Н3, Н6), 1.80–
1.95 m (2Н, Н4, Н5), 2.03–2.16 m (2Н, Н19), 2.18–2.27
m (1Н, Н3), 2.34 s (3Н, СН3para), 2.99-3.09 m (1Н,
Н2), 3.97–4.05 m (1Н, Н17), 4.49 and 4.51 s (1Н, ОН),
6.95 and 6.98 s (1Н, H16), 7.02 s (1Н, Н14), 7.23–7.33
m (5Н, Н21–25). 13С NMR spectrum, δ, ppm: 12.03 and
12.22 (С10), 12.68 and 12.75 (С9), 20.26 and 20.34
(С8), 21.33 and 21.48 (Сpara, С18), 27.56 (С5), 28.04
(С19), 29.55 (С3), 33.98 (С6), 45.59 and 45.72 (С17),
46.86 (С2), 47.16 (С4), 48.10 (С7), 49.66 and 49.75
(С1), 125.65 and 126.06 (С14), 126.07 (С23), 126.45
and 126.66 (С16), 128.01 and 128.14 (С22,24), 128.40
(С11), 128.61 and 128.65 (С21,25), 129.58 and 129.88
(С13), 130.08 and 130.18 (С20), 144.16 (С15), 150.48
and 150.64 (С12). Found, %: С 86.13; Н 9.45.
C26H34O. Calculated, %: С 86.4; Н 9.61.
ACKNOWLEDGMENTS
This work was performed with the support from the
Program “UMNIK” (no. 4799GU1/2014), partially
financed by the Program of Ural Branch of Russian
Academy of Sciences (no. 15-6-3-6). Spectral
measurements were performed with the use of equip-
ment of the Center for Joint Usage “Chemistry” of the
Institute of Chemistry of Komi Scientific Center, Ural
Branch, Russian Academy of Sciences.
2-(1-Phenylpropan-2-yl)-6-(1,7,7-trimethylbi-
cyclo[2.2.1]hept-exo-2-yl)phenol (2a). Colorless oil.
IR spectrum, ν, cm–1: 3604, 3531, 2953, 2933, 2873,
1598, 1444, 702. 1Н NMR spectrum, δ, ppm: 0.62 and
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0.80 s (3Н, СН3 ), 0.86 and 0.89 s (3Н, СН3 ), 0.93
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8
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SYNTHESIS AND ANTIRADICAL ACTIVITY OF HYBRID ANTIOXIDANTS
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