Kinetics and mechanism of the oxidation of 4-Oxo-4-arylbutanoic acids by N-bromophthalimide in aqueous acetic acid medium

Article abstract of DOI:10.1007/s10953-013-0025-7

The kinetics of oxidation of a series of substituted 4-oxobutanoic acids (Y-C₆H₄COCH₂CH₂COOH: Y = H, OCH ₃, CH₃, C₆H₅, Cl, Br or NO ₂) by N-bromophthalimide have been studied in aqueous acetic acid medium at 30 C. The total reaction is second-order, first-order each in oxidant and substrate. The oxidation rate increases linearly with [H⁺], establishing the hypobromous acidium ion, H₂O⁺Br, as the reactive species. A variation in ionic strength has no effect on the reaction rate. The order of reactivity among the studied 4-oxoacids is: 4-methoxy > 4-methyl > 4-phenyl > 4-H > 4-Cl > 4-Br > 3-NO₂. The effect of changes on the electronic nature of the substrate reveals that there is a development of positive charge in the transition state. The activation parameters have been computed from Arrhenius and Eyring plots. Based on the kinetic results, a suitable mechanism has been proposed.

Full text of DOI:10.1007/s10953-013-0025-7

J Solution Chem (2013) 42:1183–1193
DOI 10.1007/s10953-013-0025-7
Kinetics and Mechanism of the Oxidation
of 4-Oxo-4-arylbutanoic Acids by N-bromophthalimide
in Aqueous Acetic Acid Medium
•
N. A. Mohamed Farook N. M. I. Alhaji A. M. Uduman Mohideen
•
•
•
G. A. Seyed Dameen Liviu Mitu M. Abshana Begam
•
Received: 16 April 2012 / Accepted: 19 November 2012 / Published online: 27 June 2013
Ó Springer Science+Business Media New York 2013
Abstract The kinetics of oxidation of a series of substituted 4-oxobutanoic acids
(Y–C6H4COCH2CH2COOH: Y = H, OCH3, CH3, C6H5, Cl, Br or NO2) by N-bromoph-
thalimide have been studied in aqueous acetic acid medium at 30 °C. The total reaction is
second-order, first-order each in oxidant and substrate. The oxidation rate increases linearly
with [H?], establishing the hypobromous acidium ion, H2O?Br, as the reactive species. A
variation in ionic strength has no effect on the reaction rate. The order of reactivity among the
studied 4-oxoacids is: 4-methoxy [ 4-methyl [ 4-phenyl [ 4-H [4-Cl [4-Br [3-NO2.
The effect of changes on the electronic nature of the substrate reveals that there is a
development of positive charge in the transition state. The activation parameters have been
computed from Arrhenius and Eyring plots. Based on the kinetic results, a suitable
mechanism has been proposed.
Keywords Kinetics ꢀ Oxidation ꢀ 4-Oxoacids ꢀ N-bromophthalimide
1 Introduction
Among the various organic compounds employed in oxidation studies, 4-oxobutanoic acid
is an attractive substrate in terms of its enolization. In strong acid medium it undergoes
enolization and the enol form is reported to be the reactive species in its reactions with
many oxidants [1].
N. A. Mohamed Farook (&) ꢀ N. M. I. Alhaji ꢀ A. M. Uduman Mohideen ꢀ G. A. Seyed Dameen
Department of Chemistry, Khadir Mohideen College, Adirampattinam 614 701, India
e-mail: nafarook@hotmail.com; nafarook@gmail.com
L. Mitu
Department of Physics and Chemistry, University of Pitesti, Pitesti 110040, Romania
M. Abshana Begam
Department of Chemistry, Adhiyamaan College of Engineering, Hosur, India
e-mail: drnam_ejc@yahoo.com
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In recent years, studies of the oxidation of various organic compounds by N-halo
compounds in acidic medium have attracted considerable attention. They are the sources of
a positive halogen and the mechanism of these reactions depends on the nature of the
active oxidizing species, which may differ depending on the nature of halogen atom, the
groups attached to the nitrogen atom and the reaction conditions [2, 3].
The list of N-halo compounds being extensively used for kinetic studies includes
N-chloro- and N-bromo-benzenesulphonamides [4–9], N-bromo- and N-chloro-amides
[10–13], N-chloro- and N-bromo-succinimides [14–22], N-chloronicotinamide[23], N-chloro-
and N-bromo-saccharin [24–27], N-bromophthalimide [28, 29], etc., with the substrates
being keto-, oxo-, hydroxy-, amino-, and carboxylic-acids [5, 10–13, 15, 18, 20, 25],
alcohols [7, 9, 21, 24], aldehydes [16, 20, 26], ketones [8, 29], and organic sulfides/
sulfoxides [4, 6, 14, 17, 22]. However, no study involving 4-oxobutanoic acids and
N-bromophthalimide has been reported so far. 4-Oxobutanoic acids have much biological
significances and play an essential role in pharmaceutical chemistry as anti-rheumatic
agents and adjuvant arthritis suppressing agents. Keeping these points in mind, we thought
it appropriate to study the kinetics and mechanism of oxidation of a series of substituted
4-oxobutanoic acids, henceforth referred to as oxo acids {Y–C6H4COCH2CH2COOH:
Y = H (S1), OCH3 (S2), CH3 (S3), C6H5 (S4), Cl (S5), Br (S6) or NO2 (S7)} with
N-bromophthalimide (NBP). Hereunder, the results obtained in the present study are
presented and analyzed.
2 Experimental Section
All of the chemicals used were of AR grade. Acetic acid (BDH) was first refluxed over
chromic acid for 6 h and then distilled. Solutions of sodium perchlorate and perchloric acid
were prepared in double distilled water. Double distilled water was employed in all the
kinetic runs.
The methoxy-, methyl- and chloro-substituted oxo acids and N-bromophthalimide were
obtained from Sigma–Aldrich Chemical Co. The remaining oxo acids were prepared by
Friedel–Crafts acylation of the corresponding substituted benzene with succinic anhydride
[30–32]. All of the oxo acids used in this study were crystallized twice from water and their
purity was checked by their melting points.
2.1 Kinetic Studies
The reaction mixtures, containing oxo acid, acetic acid and perchloric acid solutions, were
thermally equilibrated for an hour at the desired temperature. The reaction was initiated by
the addition of a temperature-equilibrated NBP solution of the requisite concentration. The
rate of reaction was followed by determining the amount of unreacted NBP iodometrically.
All of the reactions were carried out under pseudo-first-order conditions by keeping an
excess (tenfold or greater) of [oxo acid] over [NBP]. The pseudo-first-order rate constants
(k1) were computed from linear plots of log10 [NBP] against time up to 90 % completion of
the reaction. The precision of the rate constant values is given in terms of 95 % the
confidence limit of the student’s t test [33] and the values were reproducible to within 5 %.
The stoichiometry of the reaction was determined by equilibrating each reaction mix-
ture of various [NBP]/[S1] ratios at 30 °C for 12 h, keeping the concentrations of all other
reagents constant. Estimation of the amount of unconsumed NBP revealed that one mole of
oxo acid was consumed for one mole of NBP.
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O
+
H
C H COCH CH COOH +
6
5
2
2
N
Br
+ 5H O
2
O
O
+ 3CO + 6H + HBr
NH
C H COOH +
2
2
6
5
O
1
The products were extracted with ether, dried and analyzed. Benzoic acid was identified
by its m.pt. (121 °C) and estimated quantitatively with the help of a standard curve at
kmax = 235 nm, and also tested with its characteristic spot test. Identification of the
products in the reactions of other oxo acids (S2–S7) was also made by comparing the Rf
value of the product with those of the authentic samples.
3 Results and Discussion
3.1 Order of Reaction
The pseudo-first-rate constants (k1) obtained at different initial concentrations of NBP, oxo
acid and H? are listed in Tables 1 and 2. The rates are almost independent of the initial
concentration of NBP. This fact, coupled with the excellent linear ln [NBP] versus time
plots, ensures that the order of the reaction with respect to NBP is one. The double
logarithmic plots of k1 versus [oxo acid] are excellently linear (Fig. 1, r [ 0.990), with
slope values almost equal to unity (0.98 0.01 (S1), 0.98 0.02 (S2), 1.01 0.02 (S3),
0.97 0.02 (S4), 0.97 0.03 (S5), 0.96 0.02 (S6) and 1.06 0.02 (S7)). Also, the
plots of k1 versus [oxo acid] give straight lines passing through the origin. These results
establish that the order of the reaction with respect to each oxo acid is one.
The k1 values measured at various initial concentrations of perchloric acid for the
oxidation of S1 show a linear increase (Table 1). The plot of log10 k1 versus log10 [H?] is
excellently linear (r = 0.999) with unit slope (0.97 0.02), indicating that the order of the
reaction with respect to [H?] is one. This is further evidenced by the excellent linearity
observed in the plot of k2 versus [H?], which passes through origin (Fig. 2), showing that
the reaction proceeds completely through an acid-catalyzed pathway [17]. Similar trends
have been observed for the oxidation of other oxo acids S2–S7, also with respect to
variation in the initial concentration of perchloric acid.
The rate of the reaction in the present study is unaffected by the change in the ionic
strength of the medium brought about by the addition of sodium perchlorate. The addition
of phthalimide, the reduced product of the reaction, significantly reduces the reaction rate.
The plot of 1/k1 versus [phthalimide] yields a straight line (Fig. 3, r = 0.998), suggesting a
pre-equilibrium step in which phthalimide is formed as one of the products. Similar
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Table 1 Pseudo first-order and second-order rate constants for the oxidation of 4-oxo-4-phenylbutanoic
acid (S1) by NBP in 50 % (v/v) aqueous acetic acid at 30 °C
103 [NBP] (molꢀL–1
)
102 [S1] (molꢀL–1
)
103 [H?] (molꢀL–1
)
105 k1 (s–1
)
103 k2 (Lꢀmol–1ꢀs–1
)
0.4
0.7
1.0
1.0
1.0
1.0
1.0
1.0
1.0
2.0
2.0
2.0
4.0
6.0
8.0
2.0
2.0
2.0
5.0
5.0
4.52 0.32
4.40 0.36
4.46 0.33
8.84 0.67
12.9 1.0
17.4 1.5
2.28 0.21
8.73 0.84
17.2 1.5
2.26 0.16
2.20 0.18
2.23 0.17
2.21 0.17
2.15 0.17
2.18 0.19
1.14 0.11
4.37 0.42
8.60 0.80
5.0
5.0
5.0
5.0
2.5
10.0
20.0
General conditions: ionic strength = 0.8 molꢀL–1, k2 values estimated as k1/[oxo acid]; the errors quoted in
k1 and k2 values are the 95 % confidence limits of the student’s t test
Table 2 Pseudo first-order rate constants for the oxidation of oxo acids S2–S7 by NBP in 50 % (v/v)
aqueous acetic acid at 30 °C
Oxo acid
102 [Oxo acid] (molꢀL–1
)
2.0
105 k1 (s–1 a
4.0
6.0
8.0
)
S2
S3
S4
S5
S6
S7
8.32 0.70
6.46 0.52
4.63 0.37
1.94 0.14
1.68 0.10
0.24 0.02
15.7 1.4
13.2 1.2
8.88 0.81
3.65 0.31
3.45 0.33
0.52 0.04
24.1 2.2
20.1 1.9
13.1 1.2
5.58 0.49
5.12 0.46
0.78 0.07
32.4 3.1
25.7 2.4
17.9 1.6
7.29 0.66
6.87 0.61
1.04 0.09
General conditions: [NBP] = 0.001 molꢀL–1, [H?] = 0.005 molꢀL–1, ionic strength = 0.8 molꢀL–1
As determined by iodometric technique following the disappearance of oxidant
a
conclusions have been arrived at in the N-chloronicotinamide oxidation of amino acids
[34] and N-bromoacetamide oxidation of a-hydroxy acids [11].
The involvement of free-radical intermediates in the present study can be excluded, as
the rate constant is not affected by the addition of acrylonitrile. In binary mixtures of acetic
acid and water as solvent, the rate of the reaction increases remarkably with an increase in
the proportion of acetic acid in the medium (Table 3). When the acetic acid content is
increased, the acidity of the medium increases while the dielectric constant of the medium
decreases. These two effects cause the rate of the oxidation to increase remarkably. Also, at
higher acidities, catalysis by acetate ions is untenable. The plot of log10 k2 versus the
inverse of dielectric constant is linear with positive slope (slope = 21.6, r = 0.987),
indicating an interaction between a positive ion and a dipolar molecule [35].
3.2 Effect of Substituents
The second-order rate constants for the oxidation of the selected oxo acids with NBP at
four different temperatures are collected in Table 4. Electron-releasing substituents in the
phenyl ring accelerate the rate, while electron-withdrawing substituents produce the
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1187
Fig. 1 Double logarithmic plots for the oxidation of 4-oxo-4-arylbutanoic acids with NBP (the line for S4 is
not shown for clarity purpose)
Fig. 2 Plot of second-order rate constants against [H?] for the oxidation of S1 with NBP
opposite effect. The log10 k2 values show excellent correlation with the rp values. The q
values calculated from the slopes of the Hammett plots at the four different temperatures
are also included in Table 4. A negative value of q indicates an accumulation of positive
charge at the reaction carbon center, while the magnitude of q value indicates the extent of
charge development on the carbon atom in the transition state of the rate-determining step.
The activation parameters evaluated using Arrhenius and Eyring equations are listed in
Table 5.
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Fig. 3 Plot of 1/k1 against [phthalimide] for the oxidation of S1 with NBP
Table 3 Effect of solvent composition on the rate of oxidation of 4-oxo-4-phenylbutanoic acid by NBP
Acetic acid–water (%) (v/v)
105 k1 (s–1
)
103 k2 (Lꢀmol–1ꢀs–1
)
50–50
60–40
70–30
80–20
4.46 0.33
5.24 0.46
6.12 0.64
8.27 0.79
2.23 0.17
2.72 0.23
3.06 0.27
4.14 0.40
General conditions: [S1] = 0.02 molꢀL–1, [H?] = 0.005 molꢀL–1, [NBP] = 0.001 molꢀL–1, temperature
30 °C
Table 4 Second-order rate constants for the oxidation of 4-oxo-4-arylbutanoic acids (Y–C6H5–
COCH2CH2COOH) by NBP
Y
103 k2 (Lꢀmol–1ꢀs–1
)
303 K
308 K
313 K
323 K
OMe
Me
Ph
H
4.16 0.35
3.23 0.26
2.32 0.19
2.23 0.17
0.97 0.07
0.84 0.05
0.12 0.01
-1.49 0.06
0.996
4.72 0.30
3.58 0.20
2.63 0.20
2.48 0.14
1.49 0.11
1.41 0.12
0.22 0.02
-1.26 0.07
0.992
5.20 0.40
3.97 0.32
2.83 0.25
2.72 0.23
1.94 0.15
1.84 0.17
0.33 0.02
-1.09 0.08
0.987
6.40 0.55
5.15 0.44
3.91 0.32
3.71 0.32
2.68 0.24
2.57 0.23
0.61 0.05
–0.94 0.06
0.990
Cl
Br
NO2
qa
r
General conditions: [oxo acid] = 0.02 molꢀL–1, [NBP] = 0.001 molꢀL–1, [H?] = 0.005 molꢀL–1, sol-
vent = 50 % acetic acid–50 % water (v/v)
a
These values obtained from the Hammett plots of log10 k2 versus rp
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Table 5 Activation parameters for the oxidation of 4-oxo-4-arylbutanoic acids (Y–C6H5–COCH2CH2-
COOH) by NBP
Y
Ea (kJꢀmol–1
)
DHà (kJꢀmol–1
)
-DSà (JꢀK-1ꢀmol-1
)
DGà (kJꢀmol-1
)
OCH3
CH3
C6H5
H
17.3 0.4
19.1 1.1
21.0 2.3
20.7 2.1
40.0 6.4
43.5 8.3
64.6 6.8
14.7 0.4
16.5 1.1
18.4 2.3
18.1 2.0
37.4 6.4
40.9 8.3
62.0 6.8
241.9 1.4
238.5 3.4
234.9 7.3
236.1 6.5
178.4 20.5
167.8 26.8
114.5 21.9
88.0 0.8
88.7 2.2
89.6 4.5
89.7 4.0
91.5 12.6
91.8 16.4
96.7 13.4
Cl
Br
NO2
3.3 Mechanism
In earlier studies with N-halo compounds in aqueous acetic acid medium, HOX, H2O?X
and[NH?X were suggested [3] to be the probable reactive species. In oxidation reactions
carried out with N-halo compounds, either in the absence of mineral acid or where the
reaction rates show a zero-order dependence on [H?], HOCl has been shown to be the
reactive species [36, 37]. In the present investigation, the first-order dependence on [H?]
excludes the possibility of HOCl being the oxidizing species. The possible involvement of
[NXH? as the reactive species in the present study also can be denied on the basis that:
(i) the addition of phthalimide reduces the reaction rate significantly, and (ii) the reactions
show a clear first-order dependence on [H?]. If the [NXH? species were the oxidizing
species, a fractional-order dependence would have resulted as in the case of N-chloro-
succinimide oxidation of aryl methyl and diaryl sulfides [17]. Thus, the most probable
reactive species in the present study is the hypohalous acidium ion, H2O?X, which is a
stronger electrophile than HOX. The participation of H2O?X in many electrophilic and
oxidation reactions has well been documented [18, 38]. Also, the observed increase in the
reaction rate with increase in acetic acid content in the solvent medium, and the excellent
linearity observed in the plot of log10 k2 versus inverse of dielectric constant of the
medium, may be taken as evidences for the existence of H2O?X as the reactive species
[38, 39].
Generally, ketones have been reported [40, 41] to be oxidized via enolization of the keto
group. The rate enhancement observed in the present study with increase in the acetic acid
content of the solvent medium establishes the involvement of the enol form of the oxo acid
in the reaction, as the enolization of a keto group is facilitated by a lowering of the
dielectric constant of the medium [40–42]. The negative q value obtained from the
Hammett plot indicates the formation of a carbocation in the rate-determining step.
The activation parameters are of the order expected for a bimolecular substitution reaction.
The large negative entropy of activation suggests that the transition state is more suitably
oriented than the reactants as the charge-separated transition state becomes solvated by a
sheath of solvent molecules. Based on these kinetic observations, the following mechanism
(Scheme 1) is proposed:
The rates of enolization of S1 under the present experimental conditions were deter-
mined by the bromination method [43] and it was found that the enolization is first-order
each in oxo acid and H?, but zero order in bromine. Also, the enolization rate is much
faster than the rate of oxidation of the oxo acid under identical experimental conditions.
These results establish that enolization of the oxo acid (Eqs. 2 and 3) is a necessary step
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Scheme 1 Reaction mechanism
prior to the oxidation of the substrate [40]. The interaction of the oxidizing species H2O?X
with the enol form of the 4-oxo acid in the rate-determining step (Eq. 4) leads to the
formation of intermediate (F), which then undergoes further oxidative cleavage to give the
products. Intermediates of similar type in which oxygen shows a formal valency of four
have been discussed [44, 45] in the oxidation of many organic and inorganic compounds.
The rate of the reaction is given as:
ꢁd½NBPꢂ
¼ k3½E][H2OþXꢂ
ð6Þ
dt
From Eqs. 2 and 3:
ꢁd½NBPꢂ k3K1K2½NBPꢂ½Sꢂ½Hþꢂ
¼
ð7Þ
dt
½PTH]
Equation 7 explains the first-order dependence of the reaction on [oxo acid], [NBP] and
[H?] and the negative dependence on phthalimide concentration.
The pseudo-first-order rate constant, k1, is given as:
k3K1K2½Sꢂ½Hþꢂ
k1 ¼
ð8Þ
ð9Þ
½PTHꢂ
Therefore, the second-order rate constant k2 is:
k3K1K2½Hþꢂ
k2 ¼
:
½PTHꢂ
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1191
Equation 9 substantiates the plot of k2 versus [H?] which passes through the origin
(Fig. 2).
3.4 Isokinetic Relationship
A linear relationship between entropies and enthalpies of activation is taken as evidence
that all of the reactions in the series proceed by the same mechanism [46, 47]. The slope of
such a plot has units of absolute temperature and it is called the isokinetic temperature (b),
at which all reactions in the series proceed at the same rate. The possible existence of an
isokinetic relationship in the present series of reactions was analyzed and it is found that
the correlation between DSà and DHà is excellent (r = 0.999), yielding an isokinetic
temperature of (360 7) K. As additional evidence, Exner’s method [48, 49] of verifying
the existence of an isokinetic relationship is also applied. The log–log plot of the rate
constants at two different temperatures (303 and 323 K) is excellently linear (r = 0.992)
with a slope (b) value of 0.555, corresponding to the isokinetic temperature of 364 K
according to the formula T1T2ð1 ꢁ bÞ=T1 ꢁ bT2, which is in good agreement with the
b values obtained from the DHà - DSà plots. The presence of an isokinetic relationship in
the present study implies that all the selected oxo acids are oxidized by the same
mechanism.
4 Conclusion
The above study shows that the hypobromous acidium ion (H2O?Br), formed from N-
bromosaccharin under the present experimental conditions, reacts with the enol form of
4-oxo acid in the rate determining step, giving the product. This experimental protocol
suggests that this reaction could find utility as a regioselective route for the synthesis
of benzoic acids. The order of reactivity among the studied 4-oxoacids is: 4-methoxy [
4-methyl [ 4-phenyl [ 4-H [ 4-Cl [ 4-Br [ 3-NO2.
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