Russian Journal of Applied Chemistry, Vol. 74, No. 12, 2001, pp. 2021 2026. Translated from Zhurnal Prikladnoi Khimii, Vol. 74, No. 12, 2001,
pp. 1962 1967.
Original Russian Text Copyright
2001 by Grigor’eva, Chernaya, Trusov.
CATALYSIS
Oxidation of D-Glucose to D-Gluconic
and D-Glucaric Acids Catalyzed by Sodium Nitrite
I. A. Grigor’eva, S. S. Chernaya, and S. R. Trusov
Riga Technical University, Riga, Latvia
Received January 30, 2001
Abstract Kinetics of catalytic oxidation of D-glucose in the HClO H O sulfolane system containing
4
2
NaNO was studied. Kinetic equations of the process were derived. A scheme for oxidation of D-glucose with
2
oxygen in the presence of NaNO2 was proposed.
1
Conventional oxidation of organic compounds with
oxygen in the presence of metal complexes is not al-
ways selective. Recently, alternative catalytic proce-
dures have been proposed, involving, in particular,
oxygen-containing nitrogen compounds [1, 2].
mental analysis, H NMR, and chromato-mass spec-
trometry. The total equilibrium concentration of N(III)
compounds in the liquid phase {[N(III)], M} was
determined by spectrophotometry [7] and chromato-
mass spectrometry.
Previously, we showed that alcohols are selectively
oxidized by oxygen in stronly acidic solutions con-
We found that oxidation of D-glucose under these
conditions is described by the equation
taining catalytic amounts of NaNO [3]. The reaction
rate and yield of the products increase in the presence
of organic sulfones [4].
2
NaNO2
H+
1
RCHO + O2
2
RCOOH + O2
D-glucose
D-gluconic
In this study, we used this procedure for oxidation
of monosaccharides, with D-glucose as an example,
since the products of its selective oxidation are widely
used in pharmaceutics.
acid
NaNO2
H+
R (COOH) + H O.
(I)
1
2
2
D-glucaric
acid
EXPERIMENTAL
The results of GLC and gasometry showed that
the volume of oxygen taken up and the concentration
of the oxidation products correspond to the stoichi-
The kinetics of the process was studied by the gas-
ometric procedure described in [5]. The concentrations ometry of Eq. (I). Therefore, in further studies, the
of D-glucose, D-gluconic acid, NaNO , and HClO4
were varied in the following ranges (M): 0.5 1.5, 0.5
volume of oxygen taken up was recalculated to the
concentration of the reactants by Eq. (I).
2
1
.5, 0.01 0.25, and 4.0 6.0, respectively. The partial
In the absence of sodium nitrite, all other condi-
tions being the same, D-glucose is not noticeably
oxygen pressure in the gas phase, p , was varied
O
2
5
5
from 0.2 10 to 1.0 10 Pa, and temperature, from
13 to 343 K. A mixture of HClO , water, and sul-
oxidized. At NaNO concentration from 0.075 to
2
3
4
0
.25 M, D-glucose is almost quantitatively converted
folane was used as solvent. The total pressure in the
5
within 2 min into D-gluconic acid, which is slowly
oxidized to D-glucaric acid (Fig. 1a). This makes im-
possible a kinetic study of oxidation of D-glucose to
D-gluconic acid (the first step) under these conditions.
At catalyst concentration of 0.01 0.05 M, reaction
system was kept constant at 1 10 Pa. The volume
of the liquid V and gas phase V was 5 and 80 ml,
respectively. The fact that the rate of oxygen uptake is
independent of the hydrodynamic parameters (reactor
volume, shape of its walls, frequency and amplitude
of rocking) indicates that the rate-determining step of
the process in the chemical reaction.
l
g
(
I) is appreciably slower (Fig. 1b), with the rate of the
second step (oxidation of D-gluconic acid to D-glu-
caric acid) being negligible as compared with that of
the first step up to 60% conversion of D-glucose. This
allowed kinetic study of the first step of reaction (I) at
The quantitative and qualitative composition of
the oxidation products was determined by GLC [6].
The structure of the products was confirmed by ele-
the initial NaNO concentration from 0.01 to 0.05 M.
2
1
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