Theoretical and experimental studies on selective oxidation of aromatic ketone by performic acid

Article abstract of DOI:10.1021/jp212489k

The Baeyer-Villiger (B-V) reactions of 3,4-dimethoxy acetophenone (DMOAP), 4-methyl acetophenone (MAP), and acetophenone (AP) with performic acid (PFA) in formic acid (FA) solvent have been studied by density functional theory (DFT) method. The noncatalyzed and the formic acid-catalyzed reaction paths have been calculated at the MPWB1K/6-311++G(d,p)-IEF-PCM// MPWB1K/6-311G(d,p) level of theory. On the basis of the calculations, the attack of peracid to the carbonyl carbon is rate-determining in both the noncatalyzed and acid-catalyzed paths. The selective oxidation of 3,4-dimethoxy acetophenone and 4-methyl acetophenone by performic acid into aromatic esters have been experimentally investigated. The kinetic rate constants were obtained in the temperature range of 303 to 323 K. The selectivity of product was also explained by the NBO electric charge analysis. The calculated activation energy barriers of the B-V reaction of DMOAP and MAP were in good agreement with those of experiment.

Full text of DOI:10.1021/jp212489k

Article
pubs.acs.org/JPCA
Theoretical and Experimental Studies on Selective Oxidation of
Aromatic Ketone by Performic Acid
Bo Liu, Xiang-Guang Meng,* Wei-Yi Li, Liang-Chun Zhou, and Chang-Wei Hu
Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu
610064, P. R. China
ABSTRACT: The Baeyer−Villiger (B−V) reactions of 3,4-
dimethoxy acetophenone (DMOAP), 4-methyl acetophenone
(MAP), and acetophenone (AP) with performic acid (PFA) in
formic acid (FA) solvent have been studied by density functional
theory (DFT) method. The noncatalyzed and the formic acid-
catalyzed reaction paths have been calculated at the MPWB1K/
6-311++G(d,p)-IEF-PCM// MPWB1K/6-311G(d,p) level of
theory. On the basis of the calculations, the attack of peracid
to the carbonyl carbon is rate-determining in both the
noncatalyzed and acid-catalyzed paths. The selective oxidation
of 3,4-dimethoxy acetophenone and 4-methyl acetophenone by
performic acid into aromatic esters have been experimentally
investigated. The kinetic rate constants were obtained in the
temperature range of 303 to 323 K. The selectivity of product was also explained by the NBO electric charge analysis. The
calculated activation energy barriers of the B−V reaction of DMOAP and MAP were in good agreement with those of
experiment.
many factors including the acidity of system, catalysts, way of
proton transfer, solvent, and the kind of ketones, the
mechanism of the reaction is still controversial for different
catalytic systems. Grein et al.20 thought that the first transition
state of oxidation of aliphatic ketones was rate-determining
when the formic acid was used as catalyst. Yamabe et al.21
proposed that the tetramolecular mechanism of the hydrogen
bond rearrangement and found that the second transition state
was rate-determining for the oxidation of acetone. However,
Alvarez-Idaboy et al.22 queried the role of the formic acid in the
migration step and calculated some different protonated ways.
In this work, we selected three ketones, 3,4-dimethoxy
acetophenone (DMOAP), 4-methyl acetophenone (MAP), and
acetophenone (AP), as the models of lignin, optimized the
reaction conditions. and highly selectively oxidized the ketones
to esters by performic acid. which can be readily prepared by
H2O2 and formic acid. DFT calculations combined with NBO
charge distribution analysis on transition states were employed
to understand the mechanism of the reaction in detail and
explain the selectivity of product in experiments.
1. INTRODUCTION
The Baeyer−Villiger (B−V) reaction is one class of the most
important reactions in Chemistry, which converts available
ketones to esters or lactones.1,2 The oxidation of aromatic
ketone into aromatic ester is an important B−V reaction for the
synthesis of dyes and pharmaceutical intermediates.3−6
Lignocellulose is a renewable natural biomass, which can be
converted into chemical and biofuel.7 The degradation of lignin
and its separation from the cellulose is one of most difficult
problems encountered in producing biofuel. Lignin contains
lots of units of −OH and/or −OCH3 substituted aromatic
propyl alcohol. Recently, we proposed a new route to degrade
lignin under mild conditions: aromatic alcohol could be
selectively oxidized to corresponding aromatic ketone,8 the
ketone could be selectively oxidized into ester by the B−V
reaction, then the ester could easily hydrolyzed to phenols and
alkyl carboxylic acid. In this route, the aromatic ketone transfer
into ester is the important step. The oxidation of cyclic and
aliphatic ketones to corresponding esters has been widely
studied.9−11 However, owing to the difficulty of synthesis of
aromatic esters in practice, the oxidation of aromatic ketone to
ester was seldom reported.
2. THEORETICAL CALCULATIONS
Theoretical calculations on the B−V reaction have be studied
in recent years;12−19 it is generally accepted that the B−V
reaction involves two elementary steps: (i) the attack of the
peroxyacid to the carbonyl carbon leads to a Criegee
intermediate, and (ii) the association of the carbon atom of
the adjacent carbonyl carbon with the peroxyacid oxygen atom
to form three atom ring state, then the rearrangement into the
corresponding ester. For the B−V reaction is influenced by
2.1. Computational Methods. All DFT calculations were
performed with the Gaussian03 programs.23 Geometries were
fully optimized at the B3LYP/6-311++G(d, p) level. The
Received: December 27, 2011
Revised: February 20, 2012
Published: February 23, 2012
© 2012 American Chemical Society
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Scheme 1. Non-Catalyzed B−V Reaction Path of Aromatic Ketones with PFA
Scheme 2. Formic Acid-Catalyzed B−V Reaction Path of Aromatic Ketones with PFA
Table 1. Total Electronic Energy, Enthalpy and Gibbs Free Energy Changes (in kJ/mol, at 298.15 K) of the Modeled Stationary
Points, Relative to the Isolated Reactants for the B−V Reaction of Aromatic Ketones with PFA Using FA as Catalyst and
a
Solvent
AP
MAP
DMOAP
system
ΔE
ΔH
ΔG
ΔE
ΔH
ΔG
ΔE
ΔH
ΔG
reactants
TS1
0
0
0
0
0
0
0
0
0
162.6
66.4
160.1
61.4
218.5
174.2
91.7
129.7
38.2
127.2
33.2
183.9
143.4
83.3
125.7
36.5
123.2
31.6
6.1
181.9
142.8
66.7
TS1 + CAT
Criegee
TS2 + CAT
TS2
32.4
29.9
22.7
20.3
8.6
69.3
64.3
168.1
129.0
−271.0
37.0
32.0
134.7
107.2
−293.9
31.6
26.7
45.1
−294.4
132.4
109.3
−291.3
69.7
67.3
57.6
55.1
47.6
product
−274.7
−274.7
−301.7
−301.7
−294.4
a
Level of theory: MPWB1K/6-311G++(d,p)-IEF-PCM//MPWB1K/6-311G(d,p).
vibrational frequencies were calculated at the same level to
obtain the zero-point vibrational energy (ZPVE) and identify
the stationary points as intermediates (with no imaginary
frequency) or transition states (with only one imaginary
frequency). In order to take the solvent effect into account,
single-point energies were calculated by means of the IEF-PCM
continuum model using formic acid (ε = 57.9) as the solvent
with the UFF radii at the MPWB1K/6-311++G(d,p) level. The
total electronic energies (ΔE), enthalpies (ΔH), and Gibbs free
energies (ΔG) were obtained by adding the single-point energy
in solvent and the gas-phase thermal corrections at 298.15 K at
the B3LYP/6-311G(d,p) level. Natural bond orbital (NBO)
analysis was also performed on the transition states to explain
the selectivity of products in experiments.
2.2. Computational Results and Discussion. Organic
acid played important roles in the B−V reaction; the roles
included the effects of protonation, hydrogen bond, and
solvent, which would cause different effects on the first and
second transition states. The effects of protonation and
hydrogen bond were studied by some researchers.24−26 In
fact, the formic acid was employed both as catalyst and solvent.
However, an alterative dichloromethane was used as solvent to
take the solvent effect into account by some researchers.20,27
The calculation using formic acid as solvent was not yet
studied. In this work, we employed formic acid as the actual
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reaction solvent to investigate the effect of formic acid on the
reaction of aromatic ketone with performic acid.
As shown in Schemes 1 and 2, the noncatalyzed and the
formic acid-catalyzed paths were calculated, respectively. For
the acid-catalyzed path (in Scheme 2), the formic acid would
participate in the formation of transition states to result in a
TS−cat complex. The formic acid played an important role in
the formation of both first and second transition states. It
established a passageway of transfer of hydrogen atom from the
performic acid to the carbon oxygen atom acting as a proton
transfer medium. The other role of the acid was that the joining
of formic acid also changed the geometric structure of
transition states. Compared with the noncatalyzed path, in
the acid-catalyzed mechanism, the first transition state (TS1−
cat) with a six-membered ring structure is more stable than TS1
with a four-membered ring structure.
The calculated changes of total electronic energy, enthalpy
and Gibbs free energy of acetophenone, 4-methyl acetophe-
none, and 3,4-dimethoxy acetophenone were listed in Table 1.
From Table 1, it can be seen that the presence of formic acid
decreased greatly the values of ΔE, ΔH, and ΔG of the first
transition state compared with that of the absence of formic
acid. However, in the second transition state, the complex
situation appeared: ΔG of the second transition states all
increased for the three aromatic ketones; ΔE of 4-methyl
acetophenone and 3,4-dimethoxy acetophenone obviously
decreased in Figure 1; however, the ΔE of acetophenone
Figure 2. Relative activation energy (ΔE) profiles of formic acid-
catalyzed paths for the oxidations of the aromatic ketones by PFA at
298.15 K.
the product was high (>99%); this can be explained by the
distribution of electric charge in the transition states. The
calculated atom electric charge density in TS1−cat, Criegee,
and TS2−cat were listed in Table 2. From Table 2, it can be
found that in the second transition state (TS2−cat), the electric
charge density of the carbon atom on the benzene ring adjacent
to carbonyl become 0.052, 0.038, and 0.029 for AP, MAP, and
DMOAP, respectively, while the electric charge density of the
carbon atom on methyl is still negative (−0.615, −0.612, and
−0.609). Therefore, the migration of oxygen on peracid with
negative charge would predominantly attack the phenyl carbon
rather than methyl carbon, which led to the formation of
phenyl acetate rather than methyl benzoate.
3. EXPERIMENTAL SECTION
3.1. Materials. 3,4-Dimethoxy acetophenone (DMOAP), 4-
methyl acetophenone (MAP), acetophenone (AP), 30%
hydrogen peroxide, 4-nitrotoluene, and formic acid (FA)
were all analytical grade and purchased from the commercial
sources. The formic acid was dried by B2O3 and further distilled
and purified. All other chemicals and solvents used were also
analytical grade without further purification.
3.2. Preparation of Performic Acid. H2O2 (30%, 20μL,
0.2 mmol) and formic acid (5 mL) were introduced and stirred
at constant 308 K in a closed glass reactor. The reaction sample
was periodically drawn from the reactor. The contents of
performic acid and hydrogen peroxide were determined
according to literature methods.30
3.3. UV and GC-MS Measurements. Ultraviolet−visible
absorbance measurements were implemented with a spectro-
photometer (UV-5300, Shanghai, China). The typical reaction
solution containing 0.02 mol·L−1 aromatic ketone and 0.038
mol·L−1 performic acid was kept at constant 308 K. The
concentrations of 3,4-dimethoxy acetophenone and 4-methyl
acetophenone in reaction solution were determined by
monitoring their disappearance at 310 and 256 nm,
respectively. The products had no absorption at the measuring
wavelengths. The reaction solution was analyzed by GC-MS
(Agilent, 5973 Network 6890N), The contents of ketones and
esters were quantitatively detected using 4-methyl nitrobenzene
as the internal standard reagent. Measure conditions, DB-5
capillary column; carrier gas, N2 60 cm3·min−1, He 2.0
cm3·min−1; gasification temperature, 200°C; the column
temperature is programmed to keep at 40°C for 1 min, then
rise to 40−250°C (10°C/min); injection volume, 0.1 μL.
Figure 1. Relative activation energy (ΔE) profiles of noncatalyzed and
formic acid-catalyzed paths for the oxidation of DMOAP by PFA at
298.15 K.
hardly changed. The results implied that for the ketones with a
substitute group, the changes of energies in the second
transition state were sensitive to the organic acid, especially
in the case that the transition state is rate-determining in the
B−V reaction. In this study, the first transition state was
identified as rate-determining for three aromatic ketones, as
illustrated in Figure 2. The participation of formic acid could
greatly decrease ΔE of the reaction. This result was very
different from the calculations using dichloromethane as
solvent in which for the reactions of acetophenone and 4-
methyl acetophenone with performic acid catalyzed by formic
acid the second transition state was rate-determing.27
There are two carbon atoms adjacent to the carbonyl of the
ketone. Which carbon atom and its group would migrate to the
oxygen atom in the rearrangement step? The different
migration positions might result in different products. Despite
that there were many investigations on the mechanism of B−V
oxidation, the factors that control migratory aptitude are still
not completely understood.28,29 In this work, the selectivity of
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Table 2. Calculated NBO Charge Distributions
AP
MAP
DMOAP
Criegee
system
TS1−cat
Criegee
TS2−cat
TS1−cat
Criegee
TS2−cat
TS1−cat
TS2−cat
phenyl carbon
methyl carbon
migrate oxygen
carbonyl carbon
carbonyl oxygen
−0.180
−0.657
−0.468
0.709
−0.091
−0.612
−0.311
0.612
0.052
−0.192
−0.657
−0.471
0.710
−0.105
−0.613
−0.311
0.614
0.038
−0.195
−0.657
−0.491
0.712
−0.101
−0.612
−0.314
0.616
0.029
−0.615
−0.348
0.720
−0.612
−0.340
0.709
−0.609
−0.344
0.686
−0.672
−0.720
−0.729
−0.671
−0.720
−0.733
−0.668
−0.720
−0.742
4. RESULTS AND DISCUSSION
The organic peracid is expensive and unsteady. In order to
investigate the exact kinetics, in this work, we readily prepared
the performic acid from 30% H2O2 and anhydrous formic acid.
The variation of concentration of oxidative species in the
reaction solution with reaction time were illustrated in Figure 3.
Figure 4. GC-MS profile of reaction solution after 6 h with 4-
nitrotoluene as an internal standard.
Figure 3. Variation of concentration of oxidative species vs time at 308
−1
■
▲
K. , performic acid; , H2O2. C0(H2O2) = 0.04 mol·L .
From Figure 3, it can be seen that the performic acid could
generate rapidly and acquire equilibrium in 50 min. The
equilibrium constant of eq 1 was evaluated to be 0.15 at 308 K.
The removal of water would be favorable to the formation of
performic acid.
HCOOH + H O ⇌ HCOOOH + H O
(1)
2
2
2
The products of reaction were analyzed by GC-MS. Figure 4
displayed the reaction product for the reaction of 3,4-
dimethoxy acetophenone with performic acid after 6 h analyzed
by GC-MS. The analysis results indicated that the sole product
was 3,4-dimethoxyphenyl acetate. The generation of 3,4-
dimethoxyphenyl acetate with time was quantitatively deter-
mined by GC-MS, as illustrated in Figure 5. From Figure 5, it
can be seen that this reaction was rapid and arrived at about
80% conversion in 5 h. An interesting thing was also found that
this reaction could carry out even in low oxidant concentration
compared with that of high concentration needed cases.31−33
We also found that the solvent caused an extreme effect on
the B−V reaction. The oxidation of aromatic ketones by
performic acid can not be carried out in the following solvents:
dioxane, ethanol, and dichloromethane, even in the mixture
solvent of the ratio of formic acid to dichloromethane beyond
25%. This is an unexpected thing compared with theoretical
computations in which many reaction paths were considered
Figure 5. Conversion of DMOAP to 3,4-dimethoxy phenyl acetate in
formic acid at 308 K. C0(DMOAP) = 0.02 mol·L−1; C0(PFA) = 0.038
mol·L−1.
feasible owing to the low calculated reaction energy in the
dichloromethane solvent.20,27
In order to investigate the reaction kinetics, we employed
excessive concentration of performic acid over that of aromatic
ketones to carry out the B−V reaction. The apparent first-order
rate constants kobs were calculated based on the plots of ln(C0/
Ct) vs t (Figure 6), where C0 and Ct were the concentrations of
reaction substrate ketone at time 0 and t, respectively. The
results were listed in Table 3. From Figure 6, it can be seen that
the plots of ln(C0(ketone)/Ct) vs t were all straight lines and
approximatively passed the origin (the correlative coefficients
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Figure 6. Plots of ln(C0(ketone)/Ct(ketone)) vs reaction time for the oxidations of DMOAP (a) and MAP (b) by PFA in formic acid at 308 K.
Table 3. Apparent First-Order Rate Constants kobs of
Oxidations of DMOAP and MAP by Performic Acid in
a
Formic Acid Solution at 308 K
DMOAP
C0(PFA) (mol·L−1
MAP
C0(PFA) (mol·L−1
)
104kobs (s−1
)
)
104kobs (s−1
)
0.160
0.184
0.218
0.249
0.268
5.17
6.11
7.54
9.15
9.59
0.160
0.218
0.268
0.310
0.347
0.94
1.25
1.64
2.00
2.26
̀
a
C0(DMOAP) = 0.0102 mol·L−1; C0(MAP) = 0.00925 mol·L−1
were all more than 0.995), which indicated the reaction was
first-order with respect to the concentrations of 3,4-dimethoxy
acetophenone and 4-methyl acetophenone, respectively.
The reaction rate equation can be written as follows:
α
β
□
●
Figure 7. Plots of ln kobs vs ln CA. , DMOAP; , MAP.
r = kC
C
B
(2)
A
where r is the reaction rate; k is the reaction rate constant; CA
and CB are the concentration of reagents A (performic acid)
and B (ketone), respectively; α and β are the power of CA and
CB, respectively. Owing to β = 1 (Figure 6), the apparent first-
order rate constant becomes
Table 4. Calculated Reaction Rate Constants k and the
Power α of CA at Different Reaction Temperature
DMOAP
MAP
T
(K)
104k (L·mol)−1.21
104k
s−1
α
(L·mol)−1.12s−1
α
α
k
= kC
A
(3)
303
308
313
318
323
45.0
49.7
63.1
75.8
95.2
1.35
1.24
1.16
1.16
1.13
5.64
7.68
8.04
11.8
13.0
1.22
0.99
1.16
1.18
1.06
obs
and it can be transferred into
ln k = ln k + α ln C
(4)
obs
A
Thus, according to eq 4, k and α could be obtained from the
intercept and slope of the straight line of the plot of ln kobs vs ln
CA. From Figure 7, it can be seen that the plots of ln kobs vs ln
CA were all in good linear relationship (the correlative
coefficients r > 0.998) for the oxidations of 3,4-dimethoxy
acetophenone and 4-methyl acetophenone by performic acid.
The calculated average values of α were 1.21 and 1.12 for 3,4-
dimethoxy acetophenone and 4-methyl acetophenone, respec-
tively. The reaction rate constants k were also obtained and
listed in Table 4. Further, the concentration of performic acid
in reaction solution was also detected after reaction for 1 h. It
av 1.21 0.09
av 1.12 0.07
can be found that the performic acid hardly decomposed in the
reaction process. Thus, the experimental fact of α > 1 meant
that performic acid involved in the B−V reaction would grow
to beyond one molecule in the elementary reaction path;
further, it is possible that performic acid is involved in the
formation of a hydrogen bond with water as described by
Kulkarnni et al.34
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In kinetics, the Arrhenius formula displays the relationship of
activation energy Ea and reaction rate constant k.
selectivity of products was also explained by the NBO electric
charge analysis on the migration of the phenyl carbon to the
peracid oxygen atom. The calculated activation energies were in
good agreement with those of experiment.
−E /RT
a
(5)
k = Ae
or
AUTHOR INFORMATION
■
E
RT
a
ln k = −
+ ln A
Corresponding Author
*Tel:+86 28 85462979. Fax: +86 28 85412291. E-mail:
mengxgchem@163.com.
(6)
where k is the rate constant, Ea is the activation energy, T is
temperature, R is the universal gas constant, and A is the
preexponential factor.
The experimental results displayed good linear relationship
(both of the correlation coefficients r > 0.97, Figure 8).
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work has been supported by the National Natural Science
Foundation of China (No. 21073126), the National Basic
Research Program of China (No. 2007CB210203), and the
Research Fund for the Doctoral Program of Higher Education
of China (No. 20090181110074).
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Figure 8. Plots of ln k vs 1/T. , DMOAP; , MAP.
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