Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 1, pp. 31−35.
Pleiades Publishing, Ltd., 2014.
Original Russian Text A.G. Galstyan, V.V. Lysak, G.A. Galstyan, 2014, published in Zhurnal Prikladnoi Khimii, 2014, Vol. 87, No. 1, pp. 35−39.
AND INDUSTRIAL ORGANIC CHEMISTRY
Oxidation of 2,4-Dinitrotoluene with Ozone
in the Presence of a Stop Reagent
A. G. Galstyan, V. V. Lysak, and G. A. Galstyan
Institute of Chemical Technologies, Dal’ East-Ukrainian National University, Gorodok Shorsa 17A,
Rubezhnoe, Lugansk oblast, 19011 Ukraine
Received December 5, 2013
Abstract—Liquid-phase oxidation of 2,4-dinitrotoluene with ozone in the presence of acetic anhydride as stop
reagent and manganese(II) acetate as catalyst was studied. The major products of oxidation with ozone in acetic
anhydride are 2,4-dinitrobenzyl alcohol (65.8%) and 2,4-dinitrobenzaldehyde (18.8%) in the form of the corre-
sponding acetates. A reaction scheme accounting for the results obtained is considered.
2,4-Dinitrobenzyl alcohol (2,4-DNBAl) and 2,4-dini-
trobenzaldehyde (2,4-DNB) are widely used as intermedi-
ates in ﬁ ne organic synthesis [1, 2]. 2,4-DNBAl is mainly
prepared by hydrolysis of 2,4-dinitrobenzyl chloride .
The drawbacks of this method are low product yield and
formation of large amounts of toxic chlorine-containing
This study deals with oxidation of 2,4-dinitrotoluene
(2,4-DNT) with an ozone–air mixture and is aimed to
develop a low-waste procedure for preparing 2,4-DNBAl
in a high yield.
We showed previously  that 2,4-DNT is oxidized
with ozone in an acetic acid solution in the presence of
cobalt(II) acetate to 2,4-dinitrobenzoic acid (2,4-DNBAc)
in 87.6% yield. The process cannot be stopped at the steps
of formation of 2,4-DNBAl or 2,4-DNB because of their
high reactivity in reactions with ozone.
As a continuation of these studies, we examined
the possibility of stopping the oxidation at the step of
2,4-DNBAl formation by performing the reaction in the
presence of a stop reagent, acetic anhydride, which can
convert labile intermediates into acetates, more resistant
to ozone .
Our studies showed that the major products of
ozonation at 20°C and atmospheric pressure
in acetic anhydride in the presence of sulfuric acid
and catalytic amounts of manganese(II) acetate are
2,4-dinitrobenzyl acetate (2,4-DNBAt) (65.8%) and
2,4-dinitrobenzylidene diacetate (2,4-DNBDA) (18.8%)
(see ﬁ gure). 2,4-DNBAc was detected in the solution
Oxidation of 2,4-DNT with ozone in acetic anhydride in
the presence of manganese(II) acetate at 20°С. Reaction
= 0.40, [Н
= 1.20, [O
] = 4 × 10
= 0.06 M; space velocity of the ozone–air mixture
. (с) Concentration of oxidation products and (τ) time.
(1) 2,4-DNT, (2) 2,4-DNBAt, (3) 2,4-DNBDA, (4) 2,4-DNBAc,
and (5) manganese(III) acetate.