202
MALIEVSKII
The values of
8.92
10–6 l2/(mol s) were determined from the cess; it largely determines the character of each eleꢀ
dependence of on [oxirane]o, whence it follows that mentary event. It is also noteworthy that at the final
for Ke = 1.85 l/mol [17], k3 = 4.71
10–6 l/(mol s) stage of the reaction. all the routes lead to the formaꢀ
150 ). The interaction of the two complexes leads tion of a single intermediate cyclic bipolar ion with
to the same products as in the case of the second direcꢀ intramolecular hydrogen bonding, which ion deterꢀ
k2 = 2.2
×
10–5 l/mol s and k3Kp
=
intact (albeit it is modified) throughout the entire proꢀ
×
Y
×
(
°C
tion.
For the reaction of two H complexes I in the system
octylꢀ ꢀhydroxyethyl sulfide–propylene oxide, which
leads to the same products as in the previous case
through the sulfonium salt IIa and complex II with
mines the final composition of the products.
The results reported in this paper represent only a
small fraction of the possibilities inherent in the
exchange reaction. We believe that the study of
exchange reactions involving organic compounds
containing other elements of 5a and 6a subgroups of
the periodic system is of no less interest. The prospects
for further study of reactions involving cycles, in which
the alkylene oxide oxygen atom is replaced by S or N
atom (thiirane and its derivatives, ethyleneimine and
its derivatives) are also of interest.
β
an interꢀion hydrogen bond, we have k3 = 8.2
103(exp – 17820/RT) (k3 = 4.71 10–6 l/(mol s)
150 ) against the rate constant for the reaction
of the Hꢀcomplex I with a molecule of hydroxyꢀ
ethyl sulfide 2 = 2.37 19350/RT) [17] (2.2
105(exp
10–5 l/(mol s), 150
) and k3 k2 = 0.21. This can be
×
×
(
°C
k
×
⎯
×
°С
/
explained by the fact that the steric hindrances in the
former case are higher than in the second.
The contribution of the reaction with two Hꢀcomꢀ
plexes I to the overall process rate increases with
increasing concentration of propylene oxide. At a
REFERENCES
1. A. D. Malievskii, Izv. Akad. Nauk, Ser. Khim., No. 4,
575 (2000).
β
ꢀhydroxyethyl sulfide concentration of 2.1 mol/L
2. A. D. Malievskii, Dokl. Akad. Nauk SSSR 190 (4), 884
(1970).
and that of propylene oxide of 0.4 mol/L, the share of
the route with two Hꢀcomplexes is as low as 7.4%, the
remainder being the reaction of the Hꢀcomplex I with
a second hydroxyethyl sulfide molecule (85.5%) and
unimolecular conversion of the Hꢀcomplex I (7.1%).
At a sulfide concentration of 0.6–0.9 mol/L and a proꢀ
pylene oxide concentration of ~10 mol/L, the share of
the route with two Hꢀcomplexes increases to ~70%.
When comparing the rate constants for the reaction of
two H complexes I with the corresponding rate constants
for the reaction of complexes I' + I in the presence of aceꢀ
3. A. D. Malievskii and V. V. Vints, in Proceeding of Scienꢀ
tific Seminar on Reactions of Organic Sulfur Compounds
Involving Sulfur Atom (Irkutsk, 1972) [in Russian].
4. A. D. Malievskii, V. V. Vints, and I. N. Kalugina, Izv.
Akad. Nauk SSSR, Ser. Khim., No. 2, 293 (1985).
5. A. D. Malievskii and O. I. Gorbunova, Izv. Akad. Nauk
SSSR, Ser. Khim., No. 12, 2833 (1982).
6. A. D. Malievskii and O. I. Gorbunova, Izv. Akad. Nauk
SSSR, Ser. Khim., No. 10, 2307 (1981).
7. A. D. Malievskii, O. I. Gorbunova, N. A. Bondarenko,
and E. N. Tsvetkov, Izv. Akad. Nauk SSSR, Ser. Khim.,
No. 1, 169 (1985).
8. V. V. Vints, V. N. Parfenov, A. U. Stepanyants, and
A. D. Malievskii, Izv. Akad. Nauk SSSR, Ser. Khim.,
No. 7, 1555 (1973).
9. A. D. Malievskii, V. V. Vints, and V. N. Parfenov, Izv.
Akad. Nauk SSSR, Ser. Khim., No. 7, 1599 (1973).
10. L. I. Shokina, A. D. Malievskii, and A. U. Stepanyants,
Izv. Akad. Nauk SSSR, Ser. Khim., No. 7, 1379 (1971).
'
tic and monochloroacetic acid (HA), we have k3
=
10–4 mol/(l s) [39] and k3
/k3 = 77 for the reaction
'
3.66
I' + I
8.1
×
'
k
3
'
products in the case of acetic acid and k3
=
'
×
10–3 l/(mol s) and k3
/k3 = 1720 l/mol s [40] for the
'
k
3
reaction I' + I
roacetic acid.
products in the case of monochloꢀ
From the ratios of the reaction rate constants
11. A. D. Malievskii, V. V. Vints, and N. M. Emanuel’,
'
k3 /k3, the effect of the catalytic action of the addition
of protonꢀdonor compounds is especially clear.
Dokl. Akad. Nauk SSSR 223 (5), 1180 (1975).
12. K. Reid, Properties and Reactions of Bonds in Organic
Molecules (Longmans, London,1968; Mir, Moscow,
1972).
13. A. D. Malievskii, V. V. Vints, N. G. Zarakhani, and
N. M. Emanuel, in Proceedings of the Second AllꢀUnion
Conference on Epoxide Monomers and Epoxy Resins
(Dnepropetrovsk, 1974), p. 125 [in Russian].
14. V. V. Vints and A. D. Malievskii, Izv. Akad. Nauk SSSR,
Ser. Khim., No. 6, 1407 (1977).
15. A. D. Malievskii, in Proceedings of 16th Conference on
Chemistry and Technology of Organic Sulfur Compounds
and Sour Oils (Riga, 1984) [in Russian].
In conclusion, it should be noted that this study not
only substantially complements the understanding of
exchange reactions, but also fundamentally changes
the understanding of the reactions of this type, since
an unusual and previously unknown mechanism for
the nonspecific exchange of functional groups in
organic molecules was established for the first time.
The determining effect of the structure of the preꢀ
reaction Hꢀcomplex on the course of the process as a
whole has been shown, and the role of the hydrogen
bridge O…H…O at all stages of the reaction until the
formation of end products has been elucidated. The
intermolecular hydrogen bond O2…H8…O7 remains
16. V. V. Vints and A. D. Malievskii, Izv. Akad. Nauk SSSR,
Ser. Khim., No. 2, 414 (1976).
PETROLEUM CHEMISTRY Vol. 52
No. 3
2012