Synthesis, structure and antioxidant activity of sulfur-containing tetrakisphenol

Article abstract of DOI:10.1134/S1070363210070200

3-[2-(3,5-Di-tert-butyl-4-hydroxyphenylsulfanyl)acetoxy]2,2-bis[2-(3, 5-di-tert-butyl-4-hydroxyphenylsulfanyl) acetoxymethyl]propyl 3,5-di-tert-butyl-4-hydroxyphenylsulfanylacetate was synthesized. Its structure was determined by means of ¹H an

Full text of DOI:10.1134/S1070363210070200

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 7, pp. 1341–1344. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © G.N. Nugumanova, T.A. Barsukova, S.V. Bukharov, D.B. Krivolapov, I.A. Litvinov, V.V. Syakaev, N.A. Mukmeneva, A.R. Burilov,
2
010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 7, pp. 1175–1178.
Synthesis, Structure and Antioxidant Activity
of Sulfur-Containing Tetrakisphenol
a
a
a
b
G. N. Nugumanova , T. A. Barsukova , S. V. Bukharov , D. B. Krivolapov ,
b
b
a
b
I. A. Litvinov , V. V. Syakaev , N. A. Mukmeneva , and A. R. Burilov
a
Kazan State Technological University,
ul. K. Marksa 68, Kazan, 420015 Tatarstan, Russia
e-mail: guliang1@rambler.ru
b
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center, Russian Academy of Sciences,
ul. Arbuzova 8, Kazan, 420088 Tatarstan, Russia
Received August 4, 2009
Abstract—3-[2-(3,5-Di-tert-butyl-4-hydroxyphenylsulfanyl)acetoxy]2,2-bis[2-(3,5-di-tert-butyl-4-hydroxy-
phenylsulfanyl)acetoxymethyl]propyl 3,5-di-tert-butyl-4-hydroxyphenylsulfanylacetate was synthesized. Its
1
13
structure was determined by means of Н and С NMR spectroscopy and X-ray-diffraction analysis. This
compound was found to possess high antioxidant activity in the conditions of auto-oxidation of low-pressure
polyethylene.
DOI: 10.1134/S1070363210070200
Nowadays among the existing stabilizers the
analog of widely known industrial phenol antioxidant
pentaerythritol-tetrakis-[3-(3,5-di-tert-butyl-4-oxyphe-
nyl)propionate] (Irganox 1010), in whose structure the
carbon atoms bonded with aromatic ring are
substituted by the sulfur atom.
polyfunctional sulfur-containing sterically hindered
phenols are of significant interest. The high antioxidant
effect of compounds of this type is due to the presence
in their structure of phenol and sulfide groups, which
can act both independently of each other or inhibit
synergistically the oxidation processes of polymers: to
terminate the kinetic oxidation chain in the reaction
with peroxide radicals and decompose the hydroper-
oxides along a nonradical process [1, 2].
Synthesis of compound I was carried out by reac-
tion of 2,6-di-tert-butyl-4-mercaptophenol II with
chloroacetic tetraester of pentaerythritol III under
argon in the presence of anhydrous triethylamine.
The structure and composition of compound I was
confirmed by Н and С NMR spectroscopy, X-ray
diffraction analysis, and elemental analysis.
In this work synthesis of the new sterically
hindered sulfur-containing tetrakisphenol, 3-[2-(3,5-di-
tert-butyl-4-hydroxyphenylsulfanyl)acetoxy]2,2-bis-
1
13
[
2-(3,5-di-tert-butyl-4-hydroxy-phenylsulfanyl)acetoxy-
Compound I molecule in the crystal takes a
particular position. The carbon atom С is located on a
1
methyl]propyl 3,5-di-tert-butyl-4-hydroxyphenyl-
sulfanylacetate I, was performed, and its structure and
antioxidant activity was established. This compound is
of significant interest since it is sulfur-containing
2 axis and have a tetrahedral configuration (Fig. 1).
Conformations of ester fragments are transoid and
1
2a 2a 3a
1
2b 2b 3b
gauche, torsion angles С С О С and С С О С
t-Bu
t-Bu
2
3
4
Et N
3
1
4
4
HO
t-Bu
SH + C[CH
2
OC(O)CH
2
Cl]
4
C
CH OC(O)CH S
OH
2
2
−
4Et N⋅HCl
3
t-Bu
4
II
III
I
1
341

1
342
NUGUMANOVA et al.
3b
4b
O
C
3b
2b
C
4b
C
S
6b
2b
C
O
1
5
C
C
10b
2a
C
C
8b
8b
C
O
2a
O
3a
C
3a
O
4a
S
4a
C
5
1
a
6a
C
C
0a
C
8a
C
8a
O
Fig. 1. Geometry of molecule I in crystal.
о
о
8а
3а'
8а
8а
equal 175.5(1) and 156.4(1) respectively. Fragments
H ···O (1/2 – x, –1/2 + y, 1/2 – z), d(O –H ) 0.84(4)
8
а
3а'
8а
3а'
ОССS in both substituents are in a gauche
conformation [torsion angles О С С S
О С С S , 72.1(2) and 69.4(2) ]. Bond lengths and
valence angles are given in Tables 1, 2.
Ǻ, d(H ···O ) 2.22(4) Ǻ, d(O ···O ) 2.959(2) Ǻ,
angle O H O 147(3) ; O –H ···O (–x, 1 – y, –z)
2
а
3а 4а 4а
8а 8а 3а'
о
8b
8b
3b''
and
2
b
3b 4b 4b
о
о
8b
8b
8b
3b''
d(O –H ) 0.71(4) Ǻ, d(H ···O ) 2.16(4) Ǻ, d
8
b
3b''
8b 8b 3b''
o
(O ···O 2.818(2) Ǻ, angle O H O 155(4) .
In addition, in the crystal intermolecular hydrogen
bonds O–H···O were observed between OH groups of
aryl substituents and ester groups oxygen resulting in
the three-dimensional networks (Fig. 2). The param-
The study of antioxidant activity of compound I in
the conditions of auto-oxidation of low-pressure
polyethylene (LPPE) shows that it provides essentially
longer induction period of oxidation (τ) for polymer in
comparison with high-effective industrial antioxidants
Irganox 1010 and ТB-3 [bis-(3,5-di-tert-butyl-4-
hydroxybenzyl)sulfide]. The induction periods of
8
а
eters of the hydrogen bonds are as follows: O –
Table 1. Bond lengths in the molecule of compound I
о
LPPE oxidation (200 С, 250 mm Hg) are given below:
Bond
d, Å
Bond
d, Å
4
b
5b
8a
8a
3a
8b
S –C
1.7745(17)
1.823(2)
O –C
1.387(2)
1.201(2)
1.380(2)
1.441(2)
1.332(2)
1.196(2)
1.5272(19)
4
b
4b
3a
S –C
C –O
Antioxidant (0.1 wt %)
None
τ, min
8
4
a
5a
8b
S –C
1.7785(17)
1.813(2)
C –O
4
a
4a
2a
2a
S –C
O –C
Irganox 1010
ТБ-3
60
2
b
3b
2b
2a
3a
O –C
1.3343(19)
1.4404(19)
1.5234(19)
O –C
2
b
3b
3b
35
O –C
C –O
1
2a
1
2b
Compound I
85
C –C
C –C
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 7 2010

SYNTHESIS, STRUCTURE AND ANTIOXIDANT ACTIVITY
1343
Fig. 2. Hydrogen bonds in crystal of compound I.
EXPERIMENTAL
package [4]. The figure was made by means of
PLATON program [5]. Bond lengths and bond angles
are given in Tables 1, 2.
1
13
The Н and С NMR spectra were recorded on a
Bruker AVANCE-600 spectrometer (600 and 150
MHz) relative to signals of the residual protons of
deuterated solvents.
Table 2. Bond angles in the molecule of compound I
Angle
ω, deg
Angle
ω, deg
X-Ray diffraction analysis of compound I was
performed on a Bruker Smart APEX2 automatic
diffractometer (MoKα irradiation, graphite mono-
2а
1
2а
6a 5a 4a
C C C
111.36(18)
108.33(9)
100.55(8)
102.28(8)
117.08(13)
122.85(16)
116.95(13)
125.83(16)
106.98(11)
126.29(16)
C C S
118.45(13)
121.57(13)
110.78(12)
118.45(13)
121.57(13)
122.85(16)
111.29(15)
122.77(17)
110.92(16)
2а
1
2b
10a 5a 4a
C C C
C
C S
5
b
4b 4b
3b 4b 4b
о
C S C
C C S
chromator, ω-scanning) at 20 С. Structure was solved
5
a
4a 4a
6a 5a 4a
C S C
C C S
by the direct method using SIR program [3]. The
extinction was not accounted for owing to its
negligible value. The hydrogen atoms were placed into
the calculated position and refined in a rider model.
Coordinates for the hydrogen atoms at the oxygen
atoms were revealed from the differential Fourier
charts and refined in the isotropic approximation. All
calculations were performed using WinGX program
3
b
2b 2b
10a 5a 4a
C O C
C
C S
3b 3b 2b
3b 3b 2b
O C O
O C O
3
a
2a 2a
2b 3b 4b
C O C
O C C
2
b
3b 4b
3a 3a 2a
O C C
O C O
2
b
2b
1
2a 3a 4a
O C C
O C C
3
a
3a 4a
O C C
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 7 2010

1
344
NUGUMANOVA et al.
Table 3. The main crystallographic parameters and structure
refinement details for compound I
and acidified with diluted НСl. The precipitate was
filtered off and dried in air to constant mass. Yield
о
1
1
.56 g (85%), mp 149–150 С (hexane). Н NMR spec-
Parameter
Value
trum (CDCl , δ, ppm): 1.44 s (72Н, CMe ), 3.54 s (8Н,
3
3
Color, habit
Empirical formula
Crystal system
Transparent prismatic
СН S), 4.09 s (8Н, СН О), 5.26 s (4Н, ОН), 7.28 s
2
2
C
69
H
100
O
12
S
4
13
(
3
(
1
1
1
8Н, ArH). C NMR spectrum (CDCl , δ, ppm):
0.247 q (CMe , J 126.1 Hz), 34.502 (CMe ), 38.474 t
3 3
СН О, J 142.0 Hz), 42.396 (С), 63.189 t (SСН , J
50.2 Hz), 123.811 (С ), 129.298 d (С , J 159.7 Hz),
37.097 s (С ), 154.078 d. t (С , J 3.6 Hz, J 8.7 Hz),
69.398 (С=О). Found, %: С 66.51; H 8.51; S 9.98.
3
Monoclinic
1
1
1
Space group
C2/c
2
2
1
2 1
Unit cells parameters
a = 18.3787(11),
b = 15.0469(9),
c = 27.4223(16) Å
α = 90.00
3
4
2
3
C H O S . Calculated, %: С 66.35; H 8.01; S 10.26.
6
9
100 12 4
β = 105.092(1),
o
2,6-Di-tert-butyl-4-mercaptophenol (II) was syn-
thesized by procedure [6].
γ = 90.00
3
Volume, Å
7321.9(8)
Z
4 (molecule is in particular position)
3-(2-Chloroacetoxy)-2,2-bis-(2-chloroacetoxyme-
thyl)propyl chloroacetate (III) was obtained by
procedure [7].
Molecular weight
1249.73
1.134
1.84
–
3
d
calc, g cm
Extinction coefficient,
The stabilized samples of LPPE of brand 80B
produced by OAO Kazanorgsintez were prepared by
mixing powdered polymer with acetone solution of
calculated amount of antioxidant followed by samples
drying in vacuum box to constant mass. Auto-
oxidation of LPPE was carried out on a stationary
–
1
μМо, cm
F(000)
2696
Interval θ
2.05 ≤ θ ≤ 26.00
0.02
R
int
Index measurement
interval
–22 ≤ h ≤ 22,
–18 ≤ k ≤ 18,
о
manometer apparatus by procedure [8] at 200 С and
–
33 ≤ l ≤ 33
oxygen pressure 250 mm Hg.
Reflections measured/
independent
27377/7200
REFERENCES
Number of the observed
reflections with I > 2σ(I)
Final values of diver-
gence factors
5519
1. Gorbunov, V.N., Maslova, N.N., and Gurvich, Ya.А.,
Khimiya i tekhnologiya stabilizatorov polimernykh
materialov (Chemistry and Technology of Stabilizers of
Polymer Materials), Moscow: Khimiya, 1981.
R = 0.0417
R
W
= 0.1331
R
all = 0.0571
2
.
Grassi, N. and Scott, J., Destruktsiya i stabilizatsiya
polimerov Destruction and Stabilization of Polymers,
Moscow: Mir, 1988.
R
W all = 0.1485
1.077
Fit parameter
∆
/σ
0.00
3
.
Altomare, A., Cascarano, G., Giacovazzo, C., and
Viterbo, D., Acta Crystallogr. Sect. A, 1991, vol. 47,
p. 744.
Number of refined
parameters
404
4
5
.
.
Farrugia, L.J., J. Appl. Crystal., 1999, vol. 32, p. 837.
The main crystallographic data for structure I are
given in Table 3.
Spek, A.L., Acta Crystallogr. Sect. A, 1990, vol. 46,
p. 34.
3
-[2-(3,5-Di-tert-butyl-4-hydroxyphenylsulfanyl)-
6. RF Patent no. 2075471, 1997, Russ. Zh. Khim, 1998,
16Н74P.
acetoxy]-2,2-bis-[2-(3,5-di-tert-butyl-4-hydroxyphe-
nyl-sulfanyl)acetoxymethyl]propyl 3,5-di-tert-butyl-
-hydroxyphenyl-sulfanylacetate (I). To a solution
7. Andriyanov, K.A. and Emel’yanov, V.N., Zh. Obshch.
Khim., 1963, vol. 34, no. 11, p. 3817.
4
of 1.4 g of thiol II and 0.65 g of ester III in 10 ml of
anhydrous acetone at room temperature in the argon
atmosphere was added 0.81 ml of triethylamine. The
reaction mixture was stirred for 2 h, poured into water,
8
.
Piotrovskii, K.B. and Tarasova, Z.N., Starenie i
stabilizatsiya sinteticheskikh kauchukov i vulkanizatorov
(Ageing and Stabilization of Synthetic Rubbers and
Vulcanizers), Moscow: Khimiya, 1980.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 7 2010