2 2
in the presence of H O
.24 The process involves the use of
the bisphenol at a low temperature, e.g., 0-20 °C, in the
presence of a methanol solvent and a specified amount of water.
hazardous oxidant and surfactant, reaction time of 2-3 h, and
elevated temperature of 45-50 °C. Also, the complex workup
of the product involves first chilling the product layer at 5 °C
and then boiling the crude product at 75-90 °C.
The above literature shows that several processes are
available for TBBPA manufacturing, yet it has not been possible
to develop a process that is instantaneous, gives tetrabromo-
bisphenol A in high yields and good color (white crystalline
powder) with an ease to recover the solvent from the reaction
mixture, and does not involve formation of the byproduct HBr.
The recovered solvent and alkali metal halide can be reused in
the subsequent bromination reactions. The process does not
require complex workup procedure and recrystallization of the
product.
12-16
In the fifth category,
a biphasic system comprising water, water immiscible haloge-
nated organic compound, and an oxidant, e.g., H , Cl , etc.
The oxidant oxidizes the HBr to Br , which in turn is then
the bisphenol A is brominated in
2 2
O
2
2
available to brominate more bisphenol A and its under-
brominated species. The disadvantages of these processes are
longer reaction times and the high expense of handling. Also
1
2,13
the process
involves the use of sulphuric acid (added for
).
acidification of 50% H
2
O
2
1
4-18
The sixth category
involves the bromination of bisphenol
1
4-16
17,18
using methanol
and H as oxidant. Again the drawbacks are high temperature,
long reaction times, formation of small amounts of methyl
bromide, and the use of a strong oxidising agent such as H
which is dangerous to handle.
and ethanol
solvents in a water mixture
2 2
O
2 2
O
This report presents a study of the instantaneous bromination
of bisphenol A using aqueous KBr and elemental bromine in
1
9,20
25,26
The seventh category
bromine in the presence of H
relates to bromination using
and a heterogeneous catalyst
nearly equimolar amounts forming KBr
3
as the active
2
O
2
brominating agent.
in a biphasic system. Disadvantages are the use of a strong
oxidising agent and catalyst, and the use of high temperature
Results and Discussion
(
75 °C).
The next category2
NaBrO as the brominating agent. The disadvantages of the
It is well-known that halogens do not readily go into solution,
and thus one must utilise a significant excess of these materials
in order to provide a sufficient amount of them to achieve the
results instantaneously. A number of organic ammonium
1-23
involves a mixture of NaBr and
3
process are low yields (<92.3%), the use of mineral acid (HCl),
low temperature (10-15 °C), long reaction time (4 h), and use
of surfactant which increases the cost of the product.
A recent U.S. Patent 6,613,947 has reported the bromination
of bisphenol A with bromine in a water-immiscible polar solvent
27
28
29
tribromides such as tetrabutyl, tetramethyl, cetyl, benzyltrime-
29,30
31
32
33
34
thyl,
pentyl pyridinium, pyridinium, DBU, [Bmim],
35
36
hexamethylene tetramine, and DPTBE have been used
previously in the bromination of organic compounds. The chief
drawbacks of these reagents are the use of expensive organic
ammonium cations and the use of 1/3 of its total bromine for
an aromatic electrophilic substitution-type reaction and 2/3 of
its bromine toward addition to C-C multiple bonds. Some of
the organic ammonium tribromides have phase transfer proper-
(
8) Eguchi, H.; Kubo, M.; Nagasaki, N.; Kunimoto, K. Process for
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(
5
,446,212, 1995.
(
(
(
(
(
(
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