Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 3, pp. 466−472.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
T.S. Kotel’nikova, O.A. Revkov, S.G. Voronina, A.L. Perkel, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 3,
AND INDUSTRIAL ORGANIC CHEMISTRY
The reactions of the alcoholysis of mixed anhydrides
of carboxylic acids by cyclohexanol are a main way of
formation of cyclohexyl esters of mono- and dicarboxylic
acids in the industrial process of cyclohexane oxidation
[1–4]. It was assumed that the mixed anhydrides
are produced as a result of transacylation of adipic
anhydride by free acids and they contain the residues of
all the carboxylic acids present in the reaction medium
[2, 3] including the formic acid. High relative yield of
cyclohexyl formate in the course of oxidation of the
cyclohexane was understood through the features of
the alcoholysis reaction of the mixed anhydrides with
formyl group .
For revealing pathways of the formation and
alcoholysis of the mixed anhydrides containing the
residue of formic acid the kinetics of all stages of these
reactions should be studied. At the same time the presence
in real processes (e.g., at cyclohexane oxidation ) of
more than ten compounds with carboxyl groups and also
the presence of reactive water essentially complicated
the study of the kinetics of the whole complex of
series-parallel reactions producing esters. Under these
conditions an employment of the model reactions for the
study of the ester formation is reasonable.
A target of this paper is the study of the kinetics of
the reactions proceeding at the alcoholysis of valeric
anhydride by cyclohexanol in the presence of formic acid.
Mixture of anhydrides formed in situ contains formic-
valeric anhydride including the residues of two important
acids of the oxidized cyclohexane.
Kinetics of Alcoholysis of Valeric Anhydride
by Cyclohexanol in the Presence of Formic Acid
T. S. Kotel’nikova, O. A. Revkov, S. G. Voronina, and A. L. Perkel
Kuzbass State Technical University, Kemerovo, Russia
Received July 30, 2008
Abstract—Kinetics of the reaction proceeding at the industrial process of cyclohexane oxidation are studied by
the model reaction of the alcoholysis of valeric anhydride by cyclohexanol in the presence of formic acid.
Formic acid (85%, pure for analysis) was maintained
over anhydrous MgSO
for dehydration and then
it was sublimated in a water-jet pump vacuum. For
additional drying a working solution of formic acid in
o-dichlorobenzene was maintained over the anhydrous
for 24 hours. A content of the main substance
in the used working solution determined by gas-liquid
chromatography (GLC) (after transferring in benzyl ether
according to ) was 99.3 ± 0.4% (n = 10, P = 0.95).
Technical grade cyclohexanol was puriﬁ ed from ethers
and cyclohexanone according to . The content of the
main substance in the used material by GLC data was 99.5
± 0.1%. Valeric anhydride was obtained by a treatment of
the anhydrous sodium valerate by acid chloride of valeric
acid . The product was treated by diazomethane
and subjected to rectiﬁ cation in a vacuum in an argon
ﬂ ow for removing valeric acid. The content of the main
substance in the used material by GLC data was 99.5 ±
0.1%. A solvent (o-dichlorobenzene) was of pure gtrade
and it was rectiﬁ ed .
The experiments on an interaction of the valeric
anhydride and cyclohexanol in the presence of
formic acid in the solution of o-dichlorobenzene were
conducted in a thermostated sealed ampoule. The
temperature maintained with an accuracyin of ±0.2°С.
In the previous experiments we established that the
starting rate of the reaction depended on an order
of the reagent mixing. The reproducible result was
reached by mixing of solutions of valeric anhydride