Mechanism of low-molecular alkenes interaction with sulfur-containing spatially hindered phenols under conditions of thermal modification of polymer materials

Article abstract of DOI:10.1134/S1070363215030226

Abstract Transformations in the course of high-temperature modification of polyolefins under action of sulfur-containing modifiers have been studied using hexene-1 and hexane as model compounds. Composition of products of thermolysis of bis[3-(3,5-di-tert

Full text of DOI:10.1134/S1070363215030226

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 3, pp. 659–666. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © A.P. Krysin, L.M. Pokrovskii, A.A. Nefedov, I.K. Shundrina, B.A. Selivanov, 2015, published in Zhurnal Obshchei Khimii, 2015,
Vol. 85, No. 3, pp. 498–505.
Mechanism of Low-Molecular Alkenes Interaction
with Sulfur-Containing Spatially Hindered Phenols
under Conditions of Thermal Modification
of Polymer Materials
a
a
a,b
A. P. Krysin , L. M. Pokrovskii , A. A. Nefedov ,
a
a
I. K. Shundrina , and B. A. Selivanov
a
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: krysin_ap@mailru
b
Novosibirsk State University, Novosibirsk, Russia
Received July 31, 2014
Abstract—Transformations in the course of high-temperature modification of polyolefins under action of
sulfur-containing modifiers have been studied using hexene-1 and hexane as model compounds. Composition
of products of thermolysis of bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propyl] disulfide and bis[3-(3,5-di-tert-
butyl-4-hydroxyphenyl)propyl] sulfide at 200–270°C has been elucidated by means of thermogravimetry and
gas chromatography–mass spectrometry. Mechanism of olefins modification with sulfides and disulfides
involving the formation of biradical intermediates is discussed.
Keywords: spatially hindered phenol, sulfur-containing polymer modifier, biradical, sulfur-containing olefin,
thermolysis, TOF chromatography–mass spectrometry
DOI: 10.1134/S1070363215030226
Using functional modifiers is a simple cost-
effective approach to improve the properties of polymer
materials, in particular, their resistance to organic
solvents, oil, and water as well as durability under
severe operation conditions [1]. Chemical modification
of polymers can take place either during the synthesis
hydroxyphenyl)propyl] disulfide I and bis[3-(3,5-di-
tert-butyl-4-hydroxyphenyl)propyl] sulfide II possess
strong antioxidant properties and are applied in
manufacturing stabilized polymer compositions [6].
When used in combination, compound I has enhanced
2–4 times the antioxidant action of vitamin E,
Mexidol, and other drugs [7].
(
at the chain growth stage via copolymerization with
an antioxidant bearing double C=C bond or at the
chain termination stage via interaction of the
macroradical with thiol-containing additives [2]) or
during molding of the final product (grafting of
spatially hindered phenols [1, 3]).
Disulfides can undergo thermal decomposition to
yield radical species [8]. The energy of heat-induced
cleavage of the S–S bond (60 kcal/mol) to give sulfide
radicals is noticeably lower than that of the ArO–H
bond yielding phenoxyl radical (82 kcal/mol) [9].
Studies of thermolysis kinetics of a series of phenolic
antioxidants have revealed that some disulfides are
capable of chemical modification of polymers under
conditions of their thermal processing [4]. Importantly,
such modification can be performed using standard
processing equipment.
The radicals formed upon thermal decomposition of
disulfides are oxidizers capable of interaction with
olefins and other polymer fragments. The influence of
the modifiers on the modified polymer properties is of
practical importance.
Earlier we have observed enhancement of basic
mechanical properties of glass-filled polyamide in the
Spatially hindered phenols can act as reducing
agents [5]. For instance, bis[3-(3,5-di-tert-butyl-4-
6
59

6
60
KRYSIN et al.
course of its thermal treatment in the presence of up to
wt% of disulfide I [10]. In particular, the impact
gravimetry, differential scanning calorimetry, and
pyrolytic chromatography–mass spectrometry.
1
viscosity and the strength at break have increased,
leading to the increase 1.5 times in the material wear
resistance. Larger concentrations of modifiers may be
used. Furthermore, a composition based on epoxy
resins containing 2.0–2.4 wt% of sulfur-containing
phenolic modifier TAB (a mixture of 2-tert-butyl-
phenol di- and polysulfides [11]) has been tested for
microelectronic devices protection against external
actions (including exposure to radiation) [12]. The
same modifier has been used in manufacturing
waterproof articles from epoxy resins [13].
Decomposition of compound I started at 205°C, its
thermolysis at heating at a rate 10 deg/min (200–240°C)
occurring via two pathways (Scheme 1). In particular,
disulfide I mainly decomposed via the path a (cleavage
of the S–S bond) to form a pair of identical radicals III
that were further stabilized to yield thiol IV along with
the dehydrogenation products: sulfur-containing
dienones V and VI (88% in total).
Another pathway b of the disulfide transformation
(cleavage of the –СН –S – bond) was a minor one;
2
2
however, its contribution grew at heating. In the course
of thermolysis at 240°C, that pathway yielded 6% of
the sulfur-containing dienone VII and 6% of the
sulfur-free compounds IX–XII.
The available data have revealed that modification
efficacy of the less hindered methylated phenol
disulfides is higher than that of their tert-butyl analogs
[14].
Sulfide II was stable against heating up to 250°C.
Its thermolysis at 250–270°C occurred with the
In this work we aimed to elucidate the mechanism
of chemical transformations in the course of polymers
modification with sulfur-containing phenol anti-
oxidants using the low-molecular models. Direct study
of the corresponding polymer mixtures should have
involved complicated analysis of non-volatile reaction
mixtures.
cleavage of the –CH –S– bond to yield a mixture
2
containing 52% of thiol IV, 9% of compound V, 13%
of allylphenol XI, 17% of dehydrogenation product of
the latter (XII), and other minor products (less than
%). The formation of thiols during alkyl sulfides
thermolysis has been discussed elsewhere [20].
1
Earlier studies of transformations of phenosanes
The revealed products of thermolysis of phenol
modifiers I and II pointed at the oxidative character of
the process accompanied with the transformation of
phenols into methylenequinones. In the case of the
pathway a, methylenequinones were likely formed
from the O,S-biradical. Thermolysis via the pathway b
apparently gave another biradical that was stabilized
via elimination of hydrogen from one of the fragments
of the aliphatic chain of the para-substituent to yield 4-
methyl-, 4-vinyl-, 4-allyl-, and 4-allenyl-2,6-di-tert-
butylphenols. The participation of biradicals in the
transformations of methylenequinones has been earlier
observed in [21]. Hence, thermolysis of sulfur-
containing compounds I and II likely occurred via the
biradical or the related mechanism.
(
phenol antioxidants of polypropylene) revealed that
phenosanes were oxidized to form methylenequinones
15]. Probably, the oxidation products were more
[
reactive towards polypropylene than the starting phenols.
Further it was shown that the structure of the
phenosane-derived methylenequinones was more
complex than had been expected, and those products
were prone to thermolytic decomposition [16]. Using
dimeric methylenequinones, it was demonstrated that
the process followed the radical mechanism [17].
Likely, the radicals formation led to unique properties
of phenosanes allowing for efficient modification of
polypropylene.
In this work we used hexene-1 as a low-molecular
model of a polyolefin (the alkene structure corres-
ponded to ethylene trimer formed via disproportiona-
tion chain termination), whereas disulfide I [18] and
sulfide II [19] were used as model modifiers. All the
reactants were volatile; hence, their interaction in the
course of heating could be tracked with chromato-
graphy–mass spectrometry technique.
We further studied under conditions of the high-
temperature processing the interaction of disulfide I
with hexane and hexene-1, low-molecular models
simulating polyolefins. It has been demonstrated that
both positions at the double bond of propene are
substituted with CH S– groups upon interaction with
3
methyl disulfide in the presence of boron trifluoride
etherate at 0°C [22]. The interaction of hexyl radical
with disulfides leads to non-branched sulfides [23].
The decomposition of modifiers I and II at heating
at 200–250°C was studied by means of thermo-
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MECHANISM OF LOW-MOLECULAR ALKENES INTERACTION
661
Scheme 1.
.
OH
OH
OH
O
a
2
+
.
.
S
S
SH
S
2
I
b
III
IV
.
O
O
O
O
.
SSH
SH
SH
VII
VIII
V
VI
O
OH
OH
O
IХ
Х
ХI
ХII
S
o
2
50 C
HO
IV + V + VI + ХI + ХII
2
II
These reactions have not been studied at elevated
temperature.
butylation (compounds XV and XVI in the same
ratio), the total content of products XIII–XVI in the
mixture being 75%. 4-Methyl-, 4-ethyl, 4-propyl-, and
Two groups of compounds were identified in the
reaction mixture obtained via interaction of hexene-1
with disulfide I at 240°C by means of gas chromato-
graphy–mass spectrometry. The first group consisted
of olefins (mainly branched ones), whereas the second
group mainly contained the products of interaction of
disulfide I with hexene-1 (two isomeric sulfides XIII
and XIV in the 1 : 3 ratio) and the products of de-tert-
4
-allyl-2,6-di-tert-butylphenols (1% of each) were
found in the reaction mixture as well (Schemes 2, 3).
Sulfide XIV was isolated from the reaction
mixture, whereas sulfide XIII was obtained by an
independent synthesis from sodium salt of thiol IV and
1-bromohexane. Further de-tert-butylation of com-
pound XIII in the presence of 0.05 wt% of p-
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6
62
KRYSIN et al.
Scheme 2.
OH
OH
8
7
OH
4
Br(CH ) CH
3
H+
H+
2
5
3
2
5
6
[IV]Na
1
9
1
6
11
1
2
14
S
SC H -n
S
6
13
1
0
13
15
1
7
ХIII
ХV
ХVI
OH
OH
o
o
2
40 C
C H CHCH
2
4
9
240 C
I
IV
ХIII +
ХV +
+
S
S
ХIV
ХVII
Scheme 3.
.
OH
OH
O
OC H
6 13
o
2
70 C
C H CH=CH
4 9 2
I
2
+
_
C H -t
4
9
.
.
SH
S
S
SC H
6 13
ХIХ
ХVIII
C H CH=CH
2
4
9
ХV + ХVII
toluenesulfonic acid at 180°C yielded compounds XV
and XVI.
furization of sulfur-containing spatially hindered
phenols was described earlier [24] but was not studied
under the conditions used in this work.
Reaction of hexene-1 with disulfide I at 260–280°С
gave 4-propyl- and 4-allyl-2-tert-butylphenols as the
major products (65% in total); isomers of dihexyl
sulfide were present in the mixture as well. Partial de
tert-butylation of 2,6-di-tert-butylphenol derivatives
into the corresponding derivatives of 2-tert-butyl-
phenol resulted in the formation of noticeable amounts
of O-alkylation products. The major fraction of those
products comprised six isomers of compound XVIII
We additionally studied the interaction of hexane (a
model of inert aliphatic chain of a polyolefin) with
disulfide
I
under conditions of the radical
decomposition of the latter at 240°С. Kinetics of a
similar reaction of 2,4,6-tri-tert-butylphenoxyl radical
with decane at 130°C has been studied earlier, but its
products has not been identified [25].
Hexane oligomers were not found in the reaction
mixture containing thiol IV (50%), a series of products
of compound I thermolysis, and a number of isomeric
pairs of hexyl-, heptyl-, octyl-, and nonyl-2,6-di-tert-
butylphenols along with a pair of sulfur-containing
isomers XIII and XIV in the 3 : 1 ratio. In contrast to
the above-discussed reaction of compound I with
hexene-1, the products with non-branched aliphatic
(
17% in total) containing two hexyl fragments each
along with isomeric sulfides XV and XVII (5% in
total, in the ratio of 1 : 4 with the isomer containing a
branched aliphatic chain prevailing). The observed
elimination of sulfur in the course of thermolysis of the
modifier determined the temperature range of its
application (<260°C). A similar process of desul-
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MECHANISM OF LOW-MOLECULAR ALKENES INTERACTION
663
chain (XIII and others) prevailed in the reaction
mixture. The total content of products of reaction of
disulfide I with hexane in the mixture was 5%.
dimethylethyl)-4-(3-thiopropyl)phenol IV was ob-
tained via hydrogenation of disulfide I [26].
Thermolysis of compound I. The compound was
stable under inert atmosphere up to 200°C. The ther-
molysis products were obtained via maintaining the
sample in a pyrolysis chamber at 240°C during 10 s.
The products composition was as follows: thiol IV
(73%), thiopropenylphenol V (13%), thiodienylphenol
VI (1.5%), methylenequinone XII (4.7%), and
hydrosulfide VII (6%).
To conclude, the modification of olefins with
disulfides involves the relatively inert saturated
fragments in addition to the reactive double bonds. In
particular, this leads to the formation of more complex
compounds containing aliphatic fragments covalently
linked to the phenol antioxidant. The obtained results
are useful for development of processes of targeted
modification of polymer materials with sulfur-
containing additives.
Thermolysis of compound II. The compound was
stable under inert atmosphere up to 250°C. The ther-
molysis products were obtained via maintaining the
sample in a pyrolysis chamber at 300°C during 10 s.
The products composition was as follows: thiol IV
(52%), methylenequinone XII (17%), allylphenol XI
(14%), and compound V (9%).
EXPERIMENTAL
Pyrolytic experiments and studies by means of high
resolution mass spectrometry were performed using an
Agilent 7200 Q-TOF chromatograph equipped with an
HP-5MS capillary column (30 m × 0.25 mm × 0.25 µm)
and a CDS Pyroprobe 5000 pyrolysis attachment. The
chromatography conditions are as follows: helium as
carrier gas at 1 mL/min; column temperature program:
2,6-Bis-(1,1-dimethylethyl)-4-(3-thiopropyl)phenol
(
IV). Found: М 280.1846. С Н ОS. Calculated: M
1
7
28
2
80.1855. Mass spectrum, m/z (I , %): 57 (100), 280
rel
(
74), 265 (70), 219 (45), 41 (21), 209 (17).
2
1
min at 50°C, heating from 50 to 280°C at a rate
0 deg/min, and 20 min at 280°C; evaporator
2,6-Bis(1,1-dimethylethyl)-4-(3-thiopropenyl)phenol
temperature 280°C; ions source temperature 230°C.
Mass spectrometry conditions: ionization at 70 eV,
scanning rate 10 scans/s at 30–650 Da.
(V). Found: М 278.1694. С Н ОS. Calculated: M
17 26
278.1699. Mass spectrum, m/z (I , %): 278 (79.3)
rel
+
[М ], 263 (100.0), 221 (28.4), 217 (66.5), 207 (72.3),
2
04 (21.4), 193 (37.1), 189 (27.5), 179 (41.5), 147
Studies by means of gas chromatography–mass
spectrometry were performed using an НР 5890 series
II chromatograph equipped with an HP-5MS capillary
column (30 m × 0.25 mm × 0.25 µm) and an НР 5971
mass-selective detector. The chromatography condi-
tions: helium as carrier gas at 1 mL/min; column
temperature program: 2 min at 50°C, heating from 50
to 300°C at 10 deg/min, and 30 min at 300°C;
evaporator temperature 300°C; and ions source tempe-
rature 175°C. Mass spectrometry conditions: ioniza-
tion at 70 eV, scanning rate 1.2 scans/s at 30–650 Da.
(
(
28.3), 128 (23.8), 115 (24.4), 77 (26.4), 57 (54.8), 41
70.7).
2,6-Bis(1,1-dimethylethyl)-4-(3-disulfanylallyl)-
phenol (VII). Found: М 310.1427. С Н ОS .
Calculated: M 310.1420. Mass spectrum, m/z (I , %):
310 (17) [М ], 245 (29), 189 (60), 133(16), 128 (17),
57 (100), 41 (18).
1
7
26
2
rel
+
4
-(1-Propenyl)-2,6-bis(1,1-dimethylethyl)phenol
(
X). Found: М 246.1983. С Н О. Calculated: М
1
7
26
+
2
46.1978. Mass spectrum, m/z (I , %): 246 (53) [М ],
rel
Thermogravimetric analysis was performed using a
Netzsch STA 409 PC instrument in helium atmosphere
at heating rate 10 deg/min.
231 (100), 141 (7), 129 (8), 128 (8), 115 (8), 91 (8), 57
(12), 41 (11).
4
-Allyl-2,6-bis(1,1-dimethylethyl)phenol (XII).
1
13
H and C NMR spectra were recorded using
Found: 246.1974. С Н О. Calculated: М
М
1
7
26
+
Bruker AM-400 and AV-600 instruments. Experiments
under pressure were run in a 50 mL rotating steel
pressure reactor.
246.1978. Mass spectrum, m/z (I , %): 246 (31) [М ],
rel
231 (100), 203 (4), 159 (4), 128 (3), 115 (5), 57 (8), 41(5).
α-Vinyl-2,6-bis(1,1-dimethylethyl)methylenequinone
(XII). Found: М 244.1819. С Н О. Calculated: М
Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propyl] di-
sulfide I and bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-
propyl] sulfide II (99% of the main component) were
obtained via crystallization from ethanol. 2,6-Bis(1,1-
1
7
24
244.1827. Mass spectrum, m/z (I , %): 244 (29.2)
rel
+
[М ], 201 (37.7), 187 (50.4), 173 (25.0), 159 (22.3),
145 (100.0), 129 (21.0), 128 (26.1), 57 (43.0).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 3 2015

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64
KRYSIN et al.
m (6Н, СН S), 2.68 t (2H, CH , J 11 Hz), 2.75 q
3
Interaction of disulfide I with hexane. 0.5 g of
disulfide I and 30 mL of n-hexane were placed in a
0 mL steel rotating pressure reactor; the latter was
purged with argon and sealed. The mixture was kept at
40°C during 10 h, and the obtained transparent
2
2
НН
3
(2Н, СН СН S, J 10 Hz), 5.05 s (1Н, OH), 6.99 s
3
2
НН
1
3
5
(3Н, Ar-H). C NMR spectrum (CDCl ), δ , ppm:
3 C
1
6
17
15
10
13.92 (С ), 21.28 (С ), 28. 82 (С ), 29.75 (С ),
8
14
13
7
2
30.20 (С ), 31.58 (С ), 31.99 (С ), 34.14 (С ), 34.91
9
11
12
2,6
solution was evaporated. According to gas chromato-
graphy–mass spectrometry results, the residue (0.44 g
of oily substance) contained 48% of thiol IV, 2% of
(С ), 36.65 (С ), 39.81 (С ), 124.77 (С ), 132.12
(С ), 135.57 (С ), 151.72 (С ). Mass spectrum, m/z
(I , %): 364 (47) [М ] (calculated: 364.2794), 293
1
3, 5
4
+
rel
2
,6-di-tert-butylphenol, 3% of 4-methyl-2,6-di-tert-
(11), 246 (67), 231 (84), 219 (28), 189 (100), 175 (10),
147 (14), 57 (46), 55 (18), 43 (40), 41 (36).
butylphenol, 5% of 4-ethyl-2,6-di-tert-butylphenol, 5.5%
of 4-propyl-2,6-di-tert-butylphenol, 10% (in total) of
compound XI and its two isomers, 3% of 4-thiopropyl-
Interaction of disulfide I with hexene-1 at 260–
2
70°C. A mixture of 0.8 g of disulfide I and 10 mL of
2
-tert-butylphenol XIX, 11% of high-boiling com-
hexene-1 were kept in a rotating steel pressure reactor
at 260–270°C during 8 h. The formed solution was
pounds I and II; 2% (in total) of the following eight
compounds (pairs of isomers with linear and branched
aliphatic chains in the 3 : 1 ratio): 4-hexyl-, 4-heptyl-,
evaporated in
a
vacuum. According to gas
chromatography–mass spectrometry results, the
residue (0.9 g) contained 51% of 4-propyl-2-tert-
butylphenol, 14% of 4-allyl-2-tert-butylphenol, four
isomers of 2-tert-butyl-4-(3-hexylthiopropyl)phenyl
hexyl ether (17% in total), three isomers of dihexyl
sulfide (10% in total), and 8% of isomeric sulfides XV
and XVII in the 1 : 2 ratio.
4
-octyl-, and 4-nonyl-2,6-di-tert-butylphenols; and
sulfur-containing isomers XIII and XIV. Aliphatic
hydrocarbons with the extended chain were not found.
Interaction of disulfide I with hexene-1 at 240°C.
.5 g of disulfide I and 15 mL of n-hexene-1 were
1
placed in a 50 mL steel rotating pressure reactor; the
latter was purged with argon and sealed. The mixture
was kept at 240°C during 6 h and then evaporated. The
residue (1.6 g) was distilled in a vacuum to obtain
2
-tert-Butyl-4-(3-hexylthiopropyl)phenyl hexyl
+
ether. Mass spectrum, m/z (I , %): 392(25) [М ]
rel
(
1
(
calculated: 392.3107), 274 (34), 217 (34), 190 (26),
75 (42), 147 (24), 133 (33), 57 (26), 43 (100), 41
44). С Н ОS.
0
.4 g of the olefin fraction and 1.0 g of residue.
2
5
44
Cyclododecane, two isomers of dodecene, 2-methyl-
undecane, and 5-methylundecane (the products of
condensation of two hexene-1 molecules) along with
octadecene (the trimerization product) were identified
in the olefin fraction. The presence of three isomers of
dihexyl sulfide (М 202, С Н S) was confirmed.
2,6-Di-tert-butyl-4-(3-hexylthiopropyl)phenol (XIII).
4.8 g of thiol IV was added to a solution of 0.4 g of
sodium disolved in 5 mL of methanol, methanol was
evaporated, and the mixture was kept in a vacuum
while stirring at 80°C during 1 h. 0.5 mL of DMF and
1
2
26
3
g of 1-bromopentane were added to the residue. The
The residue contained 46% of isomers XIV and
XIII in the 2.5 : 1 ratio and 31% of their mono-de-tert-
butylated isomers (XVII and XV) in the same ratio.
The following sulfur-free phenols were isolated from
the reaction mixture by means of thin-layer
chromatography and identified: 2,6-di-tert-butylphenol
and its 4-methyl, 4-ethyl, and 4-allyl derivatives (5.5%
in total). On top of that, the fraction contained 6% of
high-boiling derivatives (compounds I and II and their
de-tert-butylation products) along with 7% of branched
olefins.
suspension was stirred at 100°C during 4 h. The
reaction mass was dissolved in chloroform and twice
washed with water to get 4.8 g (68%) of dark oily
substance containing 95% of sulfide XIII (GC–MS).
The product was purified by silica gel chromatography
of the solution in chloroform to obtain colorless oily
substance. H NMR spectrum (CDCl ), δ, ppm: 0.94 t
1
3
3
(
3H, СН , J 10 Hz), 1.28–1.50 m and 1.49 s (18H,
3
НН
t-Bu); 1.59–1.69 m, 1.88–1.98 m and 2.54–2.63 m
3
(
8Н, СН S), 2.68 t (2H, CH , J 7.5 Hz), 5.1 s (1H,
2 2 НН
1
3
OH), 7.04 s (2H, Ar-H). C NMR spectrum (CDCl ),
3
17
16
15
2,6-Di-tert-butyl-4-[3-propylthio-(2-hexyl)]phenol
δ , ppm: 13.91 (С ), 22.42 (С ), 28.82 (С ), 29.94
C
1
0
8
11
12
14
(
XVII). Isolated by TLC on silica gel with a 1 : 1
(С ), 30.31 (С ), 31.23 (С ), 31.33 (С ), 31.33 (С ),
31.99 (С ), 34.14 (С ), 34.77 (С ), 124.84 (С ),
132.08 (С ), 135.64 (С ), 151.77 (С ). Mass
spectrum, m/z (I , %): 364 (47) [М ] (calculated:
1
13
7
9
2,6
CHCl –hexane mixture as eluent. H NMR spectrum
3
3
1
3,5
4
(CDCl ), δ, ppm: 0.90 t (3Н, СН СН , J 10 Hz),
3
3
2
НН
3
+
1
.26 d (3H, СН СН, J 10 Hz), 1.24–1.50 m (6H,
3
НН
rel
СН ), 1.44 s (18H, t-Bu), 1.82–1.93 m and 2.49–2.67
364.2794), 293 (11), 246 (67), 231 (84), 219 (28), 189
2
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MECHANISM OF LOW-MOLECULAR ALKENES INTERACTION
665
(
(
100), 175 (10), 147 (14), 57 (46), 55 (18), 43 (40), 41
2,6-Di-tert-butyl-4-methylene-2,5-cyclohexadien-
36). С Н ОS.
1-one. Mass spectrum, m/z (Irel, %): 161 (100), 203
2
3
40
+
(
(
49), 175 (40), 218 (28) [М ] (calculated: 218.167), 91
16), 77 (11), 115 (11), 105 (10). С Н О.
De-tert-butylation of 2,6-di-tert-butyl-4-(3-hexyl-
15
22
thiopropyl)phenol sulfide (XIII). A mixture of 3 g of
sulfide XIII and 60 mg of p-toluenesulfonic acid were
stirred at 200°C during 0.6 h and then subjected to
chromatography on silica gel eluting with a 3 : 2
chloroform–hexane mixture. The fraction with R 0.35
was evaporated to obtain 2.2 g of 2-tert-butyl-4-(3-
hexylthiopropylphenol XV. Н NMR spectrum (CDCl ),
δ, ppm: 0.92 t (3Н, СН , J 10 Hz), 1.25–1.45 m and
1
ACKNOWLEDGMENTS
Analytical studies were carried at the Center for
f
Joint Usage, Siberian Branch, Russian Academy of
Sciences. Authors are grateful to V.P. Rodionov for
assistance with the experiments run in pressurized
devices.
1
3
3
3
НН
.43 s (9Н, t-C H ), 1.55–1.65 m (2Н, CH ), 1.85–1.96
4 9 2
m (2Н, CH ), 2.51–2.59 m (4Н, CH ), 2.62 t (2Н,
2
2
3
REFERENCES
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13
1
.8 Hz), 7.09 d (1Н, Ar-H, JНН 1.8 Hz). C NMR
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1
7
16
3
C
1
5
10
8
12
2
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3,14
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7
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1
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3
3
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3
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3
1
2
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16
15
1
3
10
12
11
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9
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1
3.79 (С ), 115.06 (С ), 129.41 (С ), 133.54 (С ),
4
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rel
(
6
calculated: 252.1542), 134 (100), 107 (34), 77 (13),
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1
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24
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8
. Perevozkina, M.G., Storozhok, N.M., Krysin, A.P., and
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rel
(
91), 246 (81), 231 (57), 248 (30), 219 (27), 526 (17),
1
47 (14), 280 (8).
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(
2
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1
29 (6).
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1
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