Study of
Oxidative Degradation of Anthranilic Acid by Di-tertiary Butyl Chromate
Renuka Thakur1, Rajeev Ranjan2*
1PG Department of Chemistry,
Ranchi Women’s College, Ranchi-834001
2PG Department of Chemistry,
Ranchi College, Ranchi-834008
*Corresponding Author E-mail: rajeevran7@yahoo.com
ABSTRACT:
Di-tertiary
butyl chromate has been used to oxidize anthranilic acid in different molar
proportions and the solid products obtained have been isolated and analyzed.
Elemental analysis, IR and thermal studies have been carried out. Results of
thermogravimetric analysis have been used to ascertain the proposed composition.
Characterization of these complexes helps in ascertaining the products formed
by the oxidation of anthranilic acid.
KEYWORDS: TBC, DTA, TLC, TGA,TBA.
A number of Cr(VI) based
oxidants are being used to carry out oxidation of a wide variety of organic
substrates.1-9 Important among these are di-tertiary butyl
chromate, di-isopropyl chromate, chromium peroxide etherate, pyridine chromium
peroxide and 2,2-bipyridyl chromium peroxide. But due to various merits
di-tertiary butyl chromate (TBC) has got an edge over other Cr (VI) based
oxidants and therefore it is not only used to carry out oxidation but also for
complex formation with advantage of the associated degradation during the
process.10-23 The thermal-decomposition pattern, mechanism of
decomposition and evaluation of kinetic parameters of complexes were reported
in this paper. The simultaneous TG/DTA curves of the complexes were recorded.
Thermal analysis involves linear heating of the complexes. On increasing the
temperature there are various chemical and physical changes at definite
temperature range.
The physical and chemical changes were associated with
the change in mass and the change of heat.
MATERIAL AND METHODS:
A molar solution of tertiary butyl chromate (TBC) was
prepared by dissolving 1 gm of dry CrO2 in 1.5 ml of tertiary butyl
alcohol (TBA). This clear brown solution of the TBC was added to the
anthranilic acid dissolved in minimum volume of dioxan in different substrate
and oxidant ratio with constant stirring. The solid products RBB1,
RBB2 and RBB3 were isolated. The obtained solid products
were washed several times with dioxan, benzene and finally with acetone.
Purification of these compounds ware done by TLC. Thermogravimetric analysis
has been done by NETZSCH Thermal Analysis STA 409. Elemental analysis, IR and
thermogravimetric analysis of these products have been carried out. On
elemental and spectral analysis of these products, RBB1, RBB2
and RBB3 were identified as complexes of chromium involving the
products of oxidation as ligands (Table-1). The results have been supported by
the thermal analysis, TG and DTA. The weight loss and corresponding heat
changes confirms the expected sequence of reaction on heating.
DISCUSSION:
The products depend on strength of the
oxidant.
Above mentioned compounds have been
analysed thermogravimetrically for the evaluation of their decomposition
kinetic parameters and thermal decomposition mechanism by NETZSCH Simultaneous
Thermal Analyser STA 409. These complexes decomposed in two or three steps
involving elimination of water, forming acid etc. The regular decomposition of
RBB1 started at 100°C. First step involves loss of three molecules
of water at 100°C, second step involves loss of one molecule of formic acid at
278°C and the third step involves loss
of rest whole unit leaving behind CrO at 300°C (table-2, fig-1).
In the complex RBB2 the decomposition
started at 110°C. First step involves loss of one molecule of HCOO-
at 120°C and second step involves loss of one molecule of water at 240°C. The
third step involves the loss of whole unit leaving behind 2CrO residue at 800oC.
The DTA curve in the thermal analyzer shows two distinct exothermic peaks, one
major at 160oC due to the loss of HCOO- and the other
major at about 240oC due to loss of one molecule of water (table-3,
fig-2).
In the complexes RBB3 the DTA curve show
one distinct exothermic peak. This peak appears near 3400C. At this
temperature the whole unit starts breaking.
Chromium takes five oxygen atoms from heating
atmosphere. At 740°C the above mentioned unit was lost leaving behind CrO5
(table-4).
Thermal
analysis report of RBB1:
The thermal analysis report of RBB1 shows
the proposed formulation. The percentage of the substance left after
experiment, corresponds to the theoretical percentage of the residue and
support the presence of CrO as residue. The presence of CrO, support the
proposed formula.
Thermal analysis report of RBB2 :
The thermal
analysis of RRB2 shows the proposed formulation. The percentage of
substance left after experiment, corresponds to the theoretical percentage of
the residue and support the presence of 2CrO as the residue. The presence of
2CrO, support the proposed formula.
DTA/TG Graph of RBB1
Fig-1
DTA/TG Graph of RBB2
Fig-2
Thermal analysis report of RBB3:
In the complex RBB3 the DTA curve show one
distinct exothermic peak. This peak appears near 340°C. At this temperature the
whole unit was starting breaking. Chromium takes five oxygen atoms from heating
atmosphere forming CrO5. At 740oC the whole unit was lost
leaving behind CrO5 (table-4).
RESULTS :
From the result
of thermal analysis the total theoretical loss percentage corresponds to the
total experimental loss percentage in the proposed formula of the complex.
Hence the thermal of RBB3 show the proposed formulation. The
presence of coordinated water in some complexes were indicated by broad band in
the region 3500-3200 cm-1.24-25 A number of polynuclear
complexes of Cr have been reported previously with carboxylate anion with many
different framework.26-28
ACKNOWLEDGEMENT :
We are thankful to the Head, CIF, BIT Mesra, Ranchi,
for providing IR Spectra and elemental analysis. We are also thankful to the
Director, RDCIS, SAIL, Ranchi, for DTA/TG analysis.
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Received
on 10.11.2015 Modified on 11.12.2015
Accepted
on 18.12.2015 © AJRC All right
reserved
Asian J. Research Chem. 8(12): December 2015; Page 721-725
DOI: 10.5958/0974-4150.2015.00116.9