Reactions of enolisable ketones with dichloroisocyanuric acid in absence and presence of added chloride ions - A kinetic study

Article abstract of DOI:10.4314/bcse.v29i1.12

Kinetics of reactions of enolisable ketones (S = acetone/2-butanone) with dichloroisocyanuric acid (DCICA) were studied in aqueous acetic acid and perchloric acid media in absence and presence of added chloride ions. The reactions were found to be pseudo zero order and pseudo first order on [DCICA] in absence and presence of chloride ions respectively. Both in presence and absence of chloride ions, first order and fractional order in substrate and perchloric acid were observed respectively. An increase in the rate of reaction was observed with an increase in chloride ion concentration as well as acetic acid composition. The results were interpreted in terms of probable mechanisms involving (i) rate-determining enol formation from the conjugate acid of the ketone (SH+) in the absence of added chloride ions and (ii) rate-determining interaction of SH⁺ with the most effective molecular chlorine species produced by the hydrolysis of DCICA (rather than a rate-determining interaction of enol with chlorine) in the presence of added chloride ions, prior to the rapid steps of product formation.

Full text of DOI:10.4314/bcse.v29i1.12

Bull. Chem. Soc. Ethiop. 2015, 29(1), 129-136.
Printed in Ethiopia
DOI: http://dx.doi.org/10.4314/bcse.v29i1.12
ISSN 1011-3924
 2015 Chemical Society of Ethiopia
REACTIONS OF ENOLISABLE KETONES WITH DICHLOROISOCYANURIC ACID
IN ABSENCE AND PRESENCE OF ADDED CHLORIDE IONS – A KINETIC STUDY
1
2*
1
Y. Lakshman Kumar , R. Venkata Nadh and P.S. Radhakrishnamurti
1
Department of Chemistry, TJPS (PG) College, Guntur-522006, India
2
School of Biotechnology, Vignan University, Vadlamudi-522213, India
(
Received July 13, 2013; revised June 29, 2014)
ABSTRACT. Kinetics of reactions of enolisable ketones (S = acetone/2-butanone) with dichloroisocyanuric
acid (DCICA) were studied in aqueous acetic acid and perchloric acid media in absence and presence of added
chloride ions. The reactions were found to be pseudo zero order and pseudo first order on [DCICA] in absence and
presence of chloride ions respectively. Both in presence and absence of chloride ions, first order and fractional
order in substrate and perchloric acid were observed respectively. An increase in the rate of reaction was observed
with an increase in chloride ion concentration as well as acetic acid composition. The results were interpreted in
terms of probable mechanisms involving (i) rate-determining enol formation from the conjugate acid of the ketone
+
+
(
SH ) in the absence of added chloride ions and (ii) rate-determining interaction of SH with the most effective
molecular chlorine species produced by the hydrolysis of DCICA (rather than a rate-determining interaction of
enol with chlorine) in the presence of added chloride ions, prior to the rapid steps of product formation.
KEY WORDS: Dichloroisocyanuric acid, Acetone, 2-Butanone, Kinetics, Chloride ion, Enolisation
INTRODUCTION
Kinetics of oxidation of ketones by different N-halo oxidants like N-bromo succinimide [1, 2],
1
7
,3-dichloro-5,5’-dimethylhydantoin [3], N-chlorosaccharin [4, 5], trichloroisocyanuric acid [6,
], N-bromosaccharin [8] have received considerable attention. A thorough literature survey
showed that till the date, reactions between dichloroisocyanuric acid (DCICA) and ketones were
not studied. Hence, an attempt has been made to study the reactions of acetone and 2-butanone
with DCICA in acetic acid-perchloric acid medium both in absence and presence of added
chloride ions. The current study is aimed to learn the behavior of DCICA, i.e. whether it acts as
a halogenating agent and/or oxidizing agent with the ketones.
EXPERIMENTAL
The substrates (acetone and 2-butanone) were of AR grade and were redistilled before use.
Dichloroisocyanuric acid was obtained from Fluka. All other chemicals used were obtained
from ExcelaR (Glaxo). The reaction was followed by estimating the concentration of unreacted
DCICA by iodometry at pH 1-2.
-
+
-
3
C O
3
N
3
H(Cl)
2
+ 4I + 2H
3
C O
3
N
3
(H)
3
2
+2I +2Cl
(1)
Compared to the rates of present reaction, self decomposition rates of DCICA were
negligibly smaller under the conditions employed. The rate constants remained practically
unaltered in air or in a de-aerated atmosphere. Only a representative set of the average values of
kinetic data in aqueous acetic acid medium was presented here.
Product analysis and stoichiometry
The product analysis was carried out by using a reaction mixture of ketone (10 mmol) and
DCICA (1 mmol). Reactants were taken in acetic acid-water mixture (15:85 v/v) and the
_
*
_________
Corresponding author. E-mail: doctornadh@yahoo.co.in

130
Y. Lakshman Kumar et al.
reaction mixture was allowed to stand for 24 hours to ensure completion of the reaction. Then
the reaction mixtures were extracted with ether. The acetic acid in the ether layer was
neutralized by using saturated sodium bicarbonate solution, washed with distilled water and
dried over anhydrous sodium sulfate. Then ether layer was separated and evaporated. The
organic products were subjected to spot tests and thin layer chromatographic analysis (silica gel,
o
1
:1 mixture of benzene and light petroleum ether b.p. 40-60 C) which revealed the formation of
oxidation products as formic acid and acetic acid for acetone, and for 2-butanone the product
was acetic acid. Reaction mixtures containing varying proportions of DCICA and ketones were
equilibrated at room temperature for 24 hours in the presence of HClO . Determination of the un
4
reacted DCICA by iodometric method showed 3:2 (DCICA:ketone) stoichiometry.
+
+
RCH
2
COCH
3
+ 3H
2
OCl + 3H
2
O
RCOOH + CH
3
COOH + 3HCl + 3H
3
O
(2)
(
R = CH
3
or H)
RESULTS AND DISCUSSION
While the disappearance of DCICA in the absence of added chloride ions was pseudo-zero order
in [DCICA] (Figure 1), the same reaction in the presence of added chloride ions exhibited
pseudo-first order kinetics (Figure 2). Both in absence and presence of chloride ions, first order
+
was observed in substrate and reaction rate increased with an increase in [H ] showing a
fractional order (Tables 1 and 2).
The reaction rates were found to increase with an increase in the percentage of acetic acid in
absence of added chloride ions (Table 1). The increase in the rate of oxidation with an increase
in the polarity of the medium suggests a more polar transition state than the reactants. The
dielectric constants (D) of water-acetic acid mixtures were calculated from the dielectric
constants of pure solvents [9]. Plots of log k versus 1/D were found to be linear with positive
slopes, indicating an interaction between a positive ion and a dipolar molecule [10].
An increase in the rate of the reaction was observed with an increase in the concentration of
added chloride ions (Table 2). In the presence of the added chloride ions, the reaction proceeded
-
–
through a Cl mediated route. The plots of log k
1
versus log [Cl ] were straight lines with a slope
–
of 0.25 indicating a fractional order with respect to [Cl ].
In order to understand the intervention of free radicals, the reaction was studied in presence
of added acrylonitrile [11-13]. There was no induced polymerization of the acrylonitrile, as
there was no formation of the precipitate and also it did not affect the rate of the reaction. The
negative polymerization test indicates the absence of in situ generation of free radicals in the
reaction mixture.
Time (s)
Figure 1. Plots for zero order dependence on oxidant (in absence of chloride).
Bull. Chem. Soc. Ethiop. 2015, 29(1)

Reactions of enolisable ketones with dichloroisocyanuric acid
131
Time (s)
Figure 2. Plots for first order dependence on oxidant (in presence of chloride).
Table 1. Oxidation of acetone and 2-butanone by DCICA in absence of added chloride ions ([DCICA] =
+
o
0
.0005 M, [Ketone] = 0.005 M, [H ] = 0.1 M, temperature = 35 C, solvent composition = 15:85
(
AcOH:H O v/v).
2
8
-1
8
-1
Conc. of variant
mol)
0.00025
k
o
x 10 mol s
o
k x 10 mol s
Variant
(
(for acetone)
(for 2-butanone)
[
Oxidant]
2.4
2.3
2.3
2.3
2.3
4.8
9.8
14.2
1.1
1.7
2.3
2.8
2.3
2.6
2.7
3.6
4.6
2.3
3.3
4.0
7.3
0
0
.00050
.00075
2.5
2.5
2.5
6.6
12.5
19.4
1.2
1.8
2.5
3.9
2.5
2.6
2.9
3.2
4.8
2.5
3.6
[Substrate]
0.0050
0
0
0
.0125
.0250
.0375
[
Acid]
0.0250
0
0
0
1
2
4
5
7
.0500
.1000
.1500
5:85
5:75
5:55
5:45
0:30
35
Solvent composition
AcOH:H
(
2
O v/v)
o
Temperature ( C)
4
4
5
0
5
0
5.0
8.4
Effect of temperature on the reaction rate was studied in the temperature range 308 K to 323
K (Tables 1 and 2) and found that the rate increased with an increase in temperature. With the
help of ln k vs 1/T plots, Arrhenius equation and Gibbs-Helmholtz relationship, activation
≠
parameters like energy of activation (E
(
a
), enthalpy of activation (ΔH ), entropy of activation
≠
≠
Z
ΔS ), free energy of activation (ΔG ) and log10 P were computed (Table 3). Slow kinetics is
suggested from the values of energy of activation. Moderate values of energy of activation
support the proposed mechanisms. Highly solvated nature of transition state is manifested from
≠
≠
the positive values of ΔG and ΔH . Negative entropy explains (a) the formation of a compact
and ordered transition state with fewer degrees of freedom and (b) a fraction of collisions are
stringent leading to a slow decomposition of the rigid activated complex.
Bull. Chem. Soc. Ethiop. 2015, 29(1)

132
Y. Lakshman Kumar et al.
Table 2. Oxidation of acetone and 2-butanone by DCICA in presence of added chloride ions ([DCICA] =
–
+
o
0
.0005 M, [Substrate] = 0.005 M, [Cl ] = 0.00125 M, [H ] = 0.1 M, temperature = 35 C, solvent
composition = 15:85 (AcOH: H O v/v).
2
5
-1
5 -1
k
1
x 10 s
1
k x 10 s
Conc. of variant
mol)
Variant
(for acetone)
(for 2-butanone)
(
[
Oxidant]
0.00025
6.1
6.3
6.3
6.0
6.1
6.3
0
0
.00050
.00075
[Substrate]
0.0050
6.3
6.1
0
0
0
.0125
.0250
.0375
13.2
26.9
38.7
3.8
12.7
26.8
33.6
3.5
[Acid]
0.0250
0
0
0
.0500
.1000
.1500
5.7
6.4
9.9
6.4
4.7
6.1
6.3
6.1
-
[
Cl ]
0.00125
.00250
0
7.0
7.3
0
.0500
35
10.0
6.4
8.6
6.1
o
Temperature ( C)
4
4
5
0
5
0
11.3
13.9
24.2
10.0
12.4
21.9
Table 3. Arrhenius parameters for oxidation of acetone and 2-butanone.





E
H
−S
G
Substrate
log10
P
Z
kJ/mol
66.3
kJ/mol
63.7
J/K/mol
184.4
kJ/mol
120.5
Acetone
Acetone
3.6
6
9.6
60.5
6.9
67.1
57.9
64.3
107.7
203.9
117.2
7.6
100.2
120.7
100.4
(
in presence of chloride ions)
2
2
-Butanone
-Butanone
2.6
6
7.1
(
in presence of chloride ions)
Active oxidizing species in absence and presence of chloride ions
The reactive species of DCICA in acidic medium may be DCICA itself or HOCl or DCICAH
+
+
+
2
or H OCl . The possibilities of both unprotonated and protonated (DCICA and DCICAH ) can
be ruled out from the negative effect of cyanuric acid on the rate of reaction. Similarly, the role
of HOCl as oxidizing species in the present reaction can be ruled out from the positive effect of
+
+
[
H ] on the rate of reaction. Hence, the only choice left under acidic conditions was H
2
OCl as
+
oxidising species. The increase in rate with an increase in [H ] indicates that probably, HOCl
+
may enter into protonation equilibrium giving H
2
OCl . Thus, reactive species may therefore, be
OCl . This is in corroboration with the work of Anil Kumar and Sondu [14],
who proposed that during hydrolysis of TCICA, the predominant species was found to be HOCl
+
assumed to be H
2
+
which may enter into protonation equilibria giving H
HOCl and H
2
OCl , thus the reactive species may be
OCl . Similarly, the participation of hypohalous acidium ion in many electrophilic
+
2
substitution and oxidation reactions was reported by Khan et al. [4].
The role of chloride ion in the kinetics of the oxidation of ketones by DCICA is very critical.
With an increase in the concentration of chloride ion, an increase in the rate of the reaction was
observed. For suggesting a most probable mechanism, identification of active oxidizing species
is required. The reaction conditions will decide the nature of the active oxidizing species. The
Bull. Chem. Soc. Ethiop. 2015, 29(1)

Reactions of enolisable ketones with dichloroisocyanuric acid
133
species with oxidizing character may vary depending on pH of the medium. Based on the
+
+
experimental conditions, Cl
2 2
, HOCl, H OCl , DCICAH and DCICA itself can be the possible
oxidizing species in aqueous solution. In the case of N-halo oxidants, HOCl was the reactive
+
2
oxidant species [15, 16]. In this study, H OCl was the active oxidant in the absence of chloride
ions. In the presence of chloride ions, the reaction was found to be catalyzed by both hydrogen
and chloride ions. Hence, the molecular chlorine formed in acidic conditions can be assumed as
the effective oxidant.
Literature survey showed that when both hydrogen and chloride ions were found to catalyze
the reactions involving N-halo compounds, molecular chlorine was assumed to act as the
effective oxidant and such reports were given in the oxidation of chalcones [17] and aminoacids
[
18]. At the lower pH, molecular chlorine is the much more reactive species than hypochlorous
acid [19]. Formation of a steady and small concentration of molecular chlorine was reported
with different N-halo compounds viz., Chloramine-T [20] and N-chloro succinimide [21-26].
Rapid reactivity of the chlorine produced by different N-halo compounds was observed for
oxidation of amines [27, 28], N-substituted amides and urea [29], and glycol [30, 31].
At present, in the presence of chloride ions, an increase in rate may be attributed to the
formation of chlorine by following the given below reactions.
DCICA + H
2
O
MCICA + HOCl
(3)
(4)
MCICA + H
2
O
Cyanuric acid + HOCl
K
1
+
+
HOCl + H
H
2
OCl
(5)
(6)
K
-
3
+
H
2
OCl + Cl
Cl
2
+ H
2
O
From the rate constants, it is clear that the order of reactivity is: acetone > 2-butanone,
which fairly corroborate with the stability of these enols. In the present study, the rate
determining step is enolisation of ketones which comprises two successive stages viz., (i)
equilibrium protonation of carbonyl group and (ii) deprotonation of α-carbon of the conjugate
acid. The enolisation rate is influenced by the relative magnitudes of these two factors. Electron
releasing and withdrawing groups persuade the first and second stages respectively. The reason
for higher reaction rate with acetone compared to 2-butanone can understood from the inductive
effect of the ethyl group tightening of protons there by increasing the relative thermodynamic
≠
stability of the keto form, which is evidenced from ΔS values (Table 3). Hence the larger
content of the enol in the cases of acetone and the lesser content enol in 2-butanone is
responsible for the reduced reactivity observed with 2-butanone.
Mechanism and rate law in absence of added chloride ions
As the reaction is independent of [DCICA] in absence of chloride ions, the observed rate of
reaction is undoubtedly dependent on the rate of enolisation. Previously, many authors have
suggested that enolisation is a slow and rate determining step when the order is zero in oxidant
[
6, 7, 32, 33]. The observed negative dielectric effect indicates that the rate determining step
+
must involve an interaction between an ion (H
ketone). It has been confirmed from stoichiometry that 1.5 moles of DCICA were consumed per
mole of ketone. Solvent isotope studies in D O medium show a retardation of rate. It is well
O is a stronger acid than hydronium ion [34] and hence this observation supports
2
OCl ) and a dipole molecule (enol form of
2
+
known that D
3
the proposed mechanism.
In absence of chloride ions, the observed rate data can be rationalized when the reaction
proceeds by (a) the protonation of ketone in the acid medium to give oxonium ion, (b)
enolisation of the oxonium ion in a rate-determining step, (c) attack of enolised form of ketone
+
by H
2
OCl in a fast step to give α-monochlorinated ketone which on further attack by second
Bull. Chem. Soc. Ethiop. 2015, 29(1)

134
Y. Lakshman Kumar et al.
+
H OCl gives α-dichlorinated ketones, (d) the α-dichlorinated ketones undergo C–C cleavage by
2
+
the attack of water molecule and further attack by another H
2
OCl to form carboxylic acid(s) by
haloform reaction (or) hydrolysis of α-di chlorinated ketones to give α-dihydroxy ketones which
+
lose a water molecule to yield α-diketone and (e) attack of third H
2
OCl on α-diketone yields
formic acid and acetic acid for acetone and acetic acid for 2-butanone.
Hence, in absence of added chloride ions, the oxidation of ketones by DCICA in acid
medium gives the final products as formic acid and acetic acid in case of acetone, and acetic
acid for 2-butanone. Diketones were reported as products through a rate determining reaction
between protonated form of the ketone and oxidants – N-bromo saccharin [35], N-
chlorosaccharin [5], Bromamine-T [36] and N-bromosuccinimide [1]. As reported by the earlier
authors, the formation of diacetyl as a product of 2-butanone with these N-halogenating agents
is unlikely due to the three main reasons viz., (i) In aliphatic series, it has been observed that α-
diketone reacts with these halogenating agents much faster than the parent ketone. Separate
experiments with 2-butanone and diacetyl with TCICA have proven that the diacetyl reacts
more than seven times faster compared to parent ketone [37]. Hence diacetyl cannot be the final
product. At best, diketone can be an intermediate product which further cleaves to carboxylic
acids. (ii) In these aliphatic ketones, halogenation reactions with N-halogenating agents go
through the haloform route leading to C-C cleavage which finally yield carboxylic acids. The
reason is that cleavage occurs by the attack of water molecule on carbonyl carbon as it is much
more positive due to -bonded oxygen. The α-carbon bearing halogens has been presumed as
being more positive by those who postulated, diacetyl as final product. (iii) The possibility of α-
diketones formation only exists in N-halogenation reaction of compounds like deoxybenzoin. In
such a case, due to the two rigid phenyl systems at each end, the C–C cleavage becomes quite
difficult even though the carbonyl carbon can attract water molecule for cleavage of C–C bond.
As this requires high energy with these special compounds, attack by water on α-carbons
displaces halogens leading to diketone - benzil as the final product, because benzil cannot be
cleaved by N-halo compounds as proven by independent experiments.
Hence, at this condition, the formation of diacetyl is very unlikely and even it is formed to
small extent, it certainly cleaved to carboxylic acids. This can be further substantiated by some
of the earlier reports that carboxylic acids were reported as major products when the oxidation
occur in acid medium through a rate determining attack on the enol form of ketone by different
oxidants viz., CAT [38], bromate [39] and permanganate [40, 41]. This supports the proposed
mechanism in absence of added chloride ions.
Rate law, for the above mechanism, comes out as
DCICA + H
2
O
MCICA + HOCl
(3)
(4)
MCICA + H
2
O
Cyanuric acid + HOCl
K
1
+
+
HOCl + H
H
2
OCl
(7)
K
2
+
+
S + H
SH
(8)
(9)
+
k0
+
SH
 EN + H
+
fast1
EN + H
2
OCl    Products
S]
(10)
[
T
[S] 

1
 K [H ]
2
(I)

rate  k [SH ]
0
Bull. Chem. Soc. Ethiop. 2015, 29(1)

Reactions of enolisable ketones with dichloroisocyanuric acid
135



k K [S][H ]
0 2

k K [S] [H ]
0
2
T

(II)
1
 K [H ]
2
This rate expression is consistent with observed kinetics in the absence of chloride ion, viz., zero
order with respect to [DCICA] and first order in [ketone] and fractional order with respect to
+
[
H ].
Mechanism and rate law in presence of added chloride ions
In the presence of chloride ions, the unit order with respect to both [DCICA] and [substrate]
indicates that probably they were not involved in the formation of any kind of complex, or even
if the complex is formed it was assumed to be highly unstable. In presence of added chloride
ions, the most probable steps of ketones reaction with DCICA can be given as (i) the
protonation of ketone in the acid medium, (ii) formation of chlorine due to reaction of added
+
chloride ions with hypochloronium ion (H
2
OCl ), (iii) formation of complex in a rate
2
determining step between protonated ketone with Cl and (iv) break down of the complex by
C–C cleavage due to attack of water molecule on carbonyl carbon, leading finally to the
formation of carboxylic acid by the usual haloform route (or) the complex rapidly breaks down
in a series of steps to give dihydroxy ketone which finally cleaves to carboxylic acids.
Finally, in the presence of chloride ions, the final products were formic acid and acetic acid
for acetone whereas, it was acetic acid for 2-butanone as observed even in the absence of
chloride ions.
For the above mechanism, the rate law can be given as
K
3
+
–
H
2
OCl + Cl
Cl
2
+ H
2
O
(6)
(11)
(12)
+
k1
SH + Cl
2
 Complex
fast
Complex    Products
The rate expression consistent with observed kinetics viz., first order with respect to oxidant
+
–
and substrate, and fractional order with respect to [H ] and [Cl ] is given below.

rate  k [SH ][Cl ]
1
2


k K K [DCICA] [H ][Cl ][S]
1
2
3
T

(III)


(
1 K [Cl ]) (1 K [H ])
3
2
CONCLUSIONS
+
In the oxidation of ketones by DCICA in acid medium, hypohalous acidium ion (H
2
OCl ) and
molecular chlorine (Cl ) were the active oxidizing species in the presence and absence of added
2
chloride ions respectively. The probable mechanisms involve (i) rate-determining enol
+
formation from the conjugate acid (SH ) of the ketone in the absence of added chloride ions and
+
(
ii) rate-determining interaction of SH with the most effective molecular chlorine species in the
presence of added chloride ions. Higher oxidation rate in acetone than 2-butanone can be
attributed to inductive effect of the methyl group tightening of protons there by increasing the
relative stability of the keto form. Both in absence and presence of added chloride ions, the final
products were formic acid and acetic acid for acetone whereas, it was acetic acid for 2-butanone
due to an interaction between a positive ion and a dipolar molecule.
Bull. Chem. Soc. Ethiop. 2015, 29(1)

136
Y. Lakshman Kumar et al.
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Bull. Chem. Soc. Ethiop. 2015, 29(1)

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