3-Substituted Thietanes as Effective Inhibitors of Cumene Oxidation

Article abstract of DOI:10.1023/A:1012764404658

3-Substituted thietanes were prepared by reaction of 1,2-epithio-3-chloropropane with various nucleophiles in aqueous solutions and were characterized. The inhibiting power of these compounds in cumene oxidation was studied.

Full text of DOI:10.1023/A:1012764404658

Russian Journal of Applied Chemistry, Vol. 74, No. 1, 2001, pp. 114 117. Translated from Zhurnal Prikladnoi Khimii, Vol. 74, No. 1,
001, pp. 110 113.
Original Russian Text Copyright
2
2001 by Farzaliev, Allakhverdiev, Magerramov, Shirinova, Dzhavadova, Rzaeva, Khalilova, Aliev.
ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY
3
-Substituted Thietanes as Effective Inhibitors
of Cumene Oxidation
V. M. Farzaliev, M. A. Allakhverdiev, A. M. Magerramov, N. A. Shirinova,
L. A. Dzhavadova, I. A. Rzaeva, A. Z. Khalilova, and F. Yu. Aliev
Kuliev Institute of Chemistry of Additives, Academy of Sciences of Azerbaidzhan Republic,
Baku, Azerbaidzhan
Baku State University, Baku, Azerbaidzhan
Received February 1, 2000; in final form, August 2000
Abstract 3-Substituted thietanes were prepared by reaction of 1,2-epithio-3-chloropropane with various
nucleophiles in aqueous solutions and were characterized. The inhibiting power of these compounds in
cumene oxidation was studied.
Previously we studied antioxidant activity of vari-
ous thiiranes and thietanes. It was shown that the in-
hibiting mechanism involves both termination of an
oxidation chain by reaction with peroxy radicals with
oxidation of the inhibitors by cumyl hydroperoxide
The structure of the resulting compounds was con-
firmed by IR and 1H NMR spectroscopy and the pur-
ity, by elemental analysis and thin-layer and gas
liquid chromatography (GLC).
The IR spectra of 3-thietanyl-substituted thio-
(
CHP) and formation of substances catalyzing hydro-
ureas III and IV contain the bands in the range 670
peroxide degradation into molecular products and
readily reacting with peroxy radicals.
1
6
80, 720 730, and 1420 1435 cm , which are typi-
cal for stretching vibrations of the four-membered
thietane ring. The band in the range 1500 1520 cm 1
is assigned to stretching vibrations of the thiourea
NHC(S) fragment.
In this work we synthesized 3-substituted thietanes
and studied their antioxidant activity in cumene oxi-
dation.
1,2-Epithio-3-chloropropane (I) was prepared by
1
In the range 2.65 3.65 ppm the H NMR spectra
reaction of epichlorohydrin with thiourea in the pres-
ence of methanol [7]. Reaction of I with ammonium
thiocyanate in an aqueous solution to form 3-thietanyl
isothiocyanate (II) was studied in [8]. 3-Thietanyl-
substituted thioureas III and IV were prepared by ad-
dition of 3-thietanyl isothiocyanate to benzylamine
and morpholine, respectively:
of 3-thietanyl-substituted thioureas III and IV contain
a quintet of four protons of two equivalent methylene
groups of the thietane ring with the intensity ratio of
1
: 4 : 6 : 4 : 1. The signal of the single methine
proton of the thietane ring appears as a quintet in the
range 4.25 4.75 ppm. The broad strong signal of the
NH protons of the thiourea skeleton is observed at
7
.05 7.65 ppm. The signals of CH protons of the
S CHN=C=S + HX
S CHNHCX,
2
benzyl fragment are observed in the range 2.5
2.9 ppm. The singlet in the range 6.61 6.89 ppm is
assigned to five aromatic protons.
S
II
III, IV
where X = NHCH2
(III), N
O (IV).
Reactions of II V with CHP were performed in
chlorobenzene under nitrogen at 110 C in a tempera-
ture-controlled glass reactor. The CHP content in the
samples taken at regular intervals was determined by
iodometric titration.
3
-Thietanol (V) was prepared by reaction of 1,2-epi-
thio-3-chloropropane with sodium carbonate [9]:
Na CO
2
3
CH2
ClCH CHCH
S
2
2
CHOH.
To determine the reaction stoichiometry, CHP was
taken in excess. The stoichiometric coefficients cal-
culated by the equation
NaCl
CH2
S
I
V
1
070-4272/01/7401-0114$25.00 2001 MAIK Nauka/Interperiodica

3-SUBSTITUTED THIETANES AS EFFECTIVE INHIBITORS
115
[
CHP]0 [CHP] VO2, ml
=
,
[InH]0
(
where [CHP] and [CHP] are the initial and final
0
CHP concentrations, respectively, [InH] is the initial
0
concentration of the inhibitor) show that products
formed from a single molecule of the inhibitors cause
several thousand CHP molecules to decompose.
The kinetic parameters of the catalytic decomposi-
tion of CHP in the presence of II V are presented in
the table. High stoichiometric coefficients indicate
the catalytic nature of CHP decomposition.
t, min
Fig. 1. Kinetic curves of cumene autooxidation at T =
10 C in the presence of the tested inhibitors with the con-
1
5
6
Analysis of the kinetic parameters of reaction of
the tested compounds with CHP shows that their ac-
tivity in this reaction appreciably depends on the
nature of the substituent in a thietane molecule.
centration [InH] = (1) 0, (2, 3) 5 10 , and (4) 5 10 M.
(
V
) Oxygen volume and (t) time; the same for Fig. 2.
VO2, ml
O
2
As in the case of the reaction with cumylperoxy
radicals, compound IV is the most active in reaction
with CHP. The rate constant K and the stoichiometic
coefficient for this compound are higher by an order
of magnitude than those for the other compounds.
The study of cumene autooxidation at 110 C in the
presence of compounds II V showed (Fig. 1) that all
these thietanes inhibit the oxidation. To determine
their antioxidant power in elementary reactions re-
sponsible for inhibition of cumene oxidation, we
studied reactions of these compounds with cumylper-
oxy radicals and CHP. All the tested compounds
(
Fig. 2) inhibit initiated oxidation of cumene. The
stoichiometric coefficient of inhibition equal to the
number of oxidation chains terminated on single in-
hibitor molecule and products of its conversion was
calculated from the induction period by the equation
t, min
Fig. 2. Kinetic curves of initiated oxidation of cumene at
2
7
[
AIBN] = 2 10 , w = 2 10 M, and T = 60 C: Inhibitor
i
4
and concentration, M: (1) none; (2) II, 1 10 (3) III,
4
6
3
10 , and (4) IV, 5 10 M.
wi
f =
,
[
InH]0
tan K [RH]w
2
i
where is the induction period (s), w is the initiation
K7
=
,
i
f [InH]0
rate (under the conditions studied it is equal to 2
7
mol l 1 s ) [10].
1
1
0
where K = 1.51 l mol 1 s 1 [12], [RH] = 6.9 M.
The rate constant of the reaction of the tested in-
hibitors with peroxy radicals K was calculated form
the rate of oxygen uptake. For this purpose the kinetic
As seen from the kinetic curves of initiated oxida-
tion of cumene, the oxidation rate in the presence
of the inhibitors after the induction period (Fig. 2,
curves 2 4) is lower than that in their absence (Fig. 2,
curve 1). This indicates that products of reaction of
II V with cumylperoxy radicals are also inhibitors.
The kinetic parameters of reaction of II V with
cumylperoxy radicals are presented in the table.
curves of oxygen uptake in the [O ] vs. t coordinates
2
were transformed into the [O2] 1 vs. t coordinates.
1
From the slope of the straight line
f K [InH]
7
0
tan
=
K2 [RH]wi
As seen from the table, the stoichiometric coeffi-
the constant K was calculated by the equation
cient f and the rate constant K for II V range from
7
7
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 74 No. 1 2001

116
FARZALIEV et al.
Kinetic parameters* of reaction of 3-substituted thietanes
with cumylperoxy radicals (60 C, [AIBN] = 2 10 M)
and CHP (110 C)
of the inhibitors with CHP, but not under the action of
the initial inhibitors.
2
EXPERIMENTAL
K7 10 4
l mol 1 s 1
K
Com-
pound
f
The IR spectra were recorded in a thin layer on a
1
Specord 75-IR spectrometer. The H NMR spectra
were recorded on a Varian T-60 spectrometer operat-
ing at 60 MHz, with tetramethylsilane as the internal
reference.
II
0.96
1.86
34
0.24
2.23
2.4
7.05
2.0
20
24
225
12
53800
68600
586000
23500
III
IV
V
Thin-layer chromatography of I V was performed
on Silufol-254 plates using an ethanol hexane mixture
(
1 : 5) as the eluent. In all case a single spot was ob-
*
AIBN is azobis(isobutyrolnitrile), f is the stoichiometric coef-
served after development with iodine.
ficient of inhibition, K is the rate constant of reaction of the
7
inhibitors with peroxy radicals, K is the rate constant of the
1-Benzyl-3-(3 -thietanyl)thiourea (III). Benzyl-
reaction with CHP, and
is the catalytic factor.
amine [10.7 g (0.1 mol)] was mixed with 3-thietanyl
isocyanate [13.1 g (0.1 mol)]. The reaction mixture
slightly warmed up. Crystalline target product was
isolated after the reaction mixture was cooled to room
temperature and diluted with benzene. The reaction
course was monitored by TLC and IR spectroscopy.
.24 to 34 and from 2.0 to 7.05 10 4 l mol 1 s , re-
1
0
spectively. Analysis of the kinetic parameters of reac-
tion of II V with cumylperoxy radicals shows that the
reactivity of these compounds strongly depends on the
nature of the substituents at the thietane ring. Com-
pound IV, unlike the other inhibitors, repeatedly ter-
minates the oxidation chains (f = 34) and exhibits very
The yield of III was 24 g (87%), mp 165 C, R =
0
f
.86.
high reactivity with respect to cumylperoxy radicals
(
Found, %: C 55.25, H 5.67, N 11.92, S 27.16.
C11H44N2S2.
K7 = 7.05 10 4 l mol 1 s ).
1
Calculated, %: C 55.42, H 5.92, N 11.75, S 26.90.
Thus, all the tested inhibitors actively decompose
CHP in three steps (Fig. 3): the first step is very slow
the induction period), the second is fast and auto-
Compound IV was prepared similarly in a 17.7 g
81%) yield from morpholine [8.7 g (0.1 mol)] and
-thietanyl isothiocyanate [13.1 (0.1 mol)]; mp 165
(
(
3
1
catalytic, and the third is the final step of CHP de-
gradation. The first two steps last different times
depending on initial concentrations of hydroxperoxide
and inhibitor. The induction period shortens with in-
creasing the hydroperoxide concentration. The shape
of the curves of CHP autocatalytic decomposition in-
dicates that CHP decomposes under the action of
products formed in the first slow step of the reaction
66 C, R = 0.80.
f
Found, %: C 51.21, H 7.75, N 14.85, S 17.37.
C H N OS .
8
14
2
2
Calculated, %: C 51.58, H 7.58, N 15.04, S 17.21.
Cumyl hydroperoxide was purified by the known
procedure [13] with subsequent distillation. Chloro-
benzene and cumene were treated with concentrated
sulfuric acid [14] to remove impurities. The CHP con-
centration was determined by iodometric titration [15].
Decomposition of CHP at 110 C in a chlorobenzene
solution was studied in glass bubbling reactor under
an inert atmosphere. The concentration of CHP and
the tested compounds was varied from 0.23 to 0.45
and from 0.5 10 4 to 5 10 6 M, respectively.
Cumene oxidation initiated by AIBN was studied on a
[RCOOH], M
manometric unit [10]. The rate constant of the initia-
tion at 60 C is K = 1.0 10 5
s
1
[11]. The initiator
t, min
concentration in all experiments was constant (2
Fig. 3. Kinetic curves of CHP decomposition at T = 110 C
under the action of V. [InH] 5 10 M. ([ROOH]) Concen-
tration and (t) time.
2
5
10 M). The concentration of the inhibitors ranged
from 1 10 to 5 10 6 M.
4
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3-SUBSTITUTED THIETANES AS EFFECTIVE INHIBITORS
117
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