CHEM. RES.

CHINESE UNIVERSITIES 2011, 27(3), 503—507

Hydroxylation of Benzene to Phenol via Hydrogen Peroxide in

Hydrophilic Triethylammonium Acetate Ionic Liquid

HU Xiao-ke, ZHU Liang-fang, GUO Bin, LIU Qiu-yuan, LI Gui-ying and HU Chang-wei∗
Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University,
Chengdu 610064, P. R. China

Abstract A new Fenton-like system in a medium of hydrophilic triethylammonium type of ionic liquid(IL) was
used for the hydroxylation of benzene to phenol. The triethylammonium acetate([Et3NH][CH3COO]) IL exhibited re-
tardation performance for the decomposition of H2O2 and protection performance for the further oxidation of phenol,
thus the yield and selectivity to phenol were promoted greatly. The acidity of the system was proved to be an impor-
tant factor for the selectivity to phenol. The utilization of H2O2 and the selectivity to phenol, as well as the Turnover
number(TON) of the catalyst were effectively enhanced by a benzene-[Et3NH][CH3COO] bi-phase system. The cata-
lyst with [Et3NH][CH3COO] IL was recycled with stable catalytic performance.
Keywords Hydrophilic; Ionic liquid; Fenton-like; Hydroxylation
Article ID 1005-9040(2011)-03-503-05

1 Introduction parison with the aqueous-hydrophobic IL biphasic system, the

separation of phenol from H2O2(an oxidant could also oxidize
As a one-step and environmentally friendly process, the phenol), as well as the catalyst was achieved in benzene-H2O2
direct hydroxylation of benzene to phenol with hydrogen pe- system.
roxide has been extensively studied. The investigation of the In this work, several hydrophilic ILs were synthesized and
solvent effect is interesting and has been performed by several used as the media for a Fenton-like reaction system for the
groups. For example, water is the solvent in traditional aqueous hydroxylation of benzene to phenol with the aim of exploring
Fenton system[1], acetonitrile and acetic acid are used as the the role of IL in the reaction. A simple hydrophilic IL, triethy-
solvents for most of the catalyzed hydroxylation reactions[2―9]. lammonium acetate([Et3NH][CH3COO]) was reported as a
Sulfolane is believed to form complexes with phenolic com- proper medium for the hydroxylation of benzene to phenol. The
pounds inducing increased selectivity to phenol[10]. A bi-phase effect of the nature of the cations and anions of ILs, the acidity
system involving water and acetonitrile was developed to de- of the system, the utilization of H2O2, as well as the recycle of
crease the over-oxidation of phenol[11]. Ionic liquid(IL), as a the catalyst with the IL were investigated in detail.
promising “green solvent”[12,13] has been, however, rarely re-
ported as the medium for the hydroxylation of benzene with 2 Experimental
hydrogen peroxide. Peng et al.[14] reported an
aqueous-[Cnmim][X](n=4,8,10; X=PF6, BF4) IL system for this 2.1 Synthesis of Ionic Liquids
reaction. In this bi-phase system, both the catalyst and benzene
[Et3NH][CH3COO] was synthesized according to the lite-
were dissolved in IL while H2O2 was mainly dissolved in
rature[16]. In a 250 mL round-bottom flask equipped with a
aqueous phase. The produced phenol was extracted into water
reflux condenser and a magnetic stirrer, glacial acetic acid was
phase, minimizing the over-oxidation. However, the high cost
dropped slowly to a stoichiometric amount of triethylamine in
and difficulty in purification for those hydrophobic ILs have
the presence of water with stirring at 80 ºC within 2 h. The
limited their application. It is supposed that a hydrophilic IL
water and a little amount of unreacted substrates were separated
would also function as the medium for the hydroxylation of
by rotary evaporator, and then the product was dried at 80 ºC in
benzene. Compared to those of products formed in the common
vacuum(666.61 Pa) until the residue remained constant. The
solvents, the selectivity of the product is expected to increase
yield of [Et3NH][CH3COO] was 96%. 1H MNR(DMSO-d6), δ:
by adjusting the cations and anions of ILs[15]. The bi-phase
1.16(t, 9H), 1.87(s, 3H), 3.02(m, 6H), 8.42(s, 1H). Other trie-
system, which could remarkably improve the over-oxidation in
thylammonium ILs, with NO3–, HSO4–, ClO4–, H2PO4–,
hydroxylation by separating the product and the catalyst, could
C2H5COO– or C3H7COO– as the anions, were synthesized via
also be constructed by the excessive benzene and the hydro-
the same process as that for [Et3NH][CH3COO] with the cor-
philic IL containing water. In such a system, benzene acts as
responding acids as the source of the anions.
not only the recycled reactant but also the extractant. In com-
Ionic liquid 1-n-butyl-3-methylimidazolium acetate
———————————
*Corresponding author. E-mail: [email protected]; [email protected]
Received April 12, 2010; accepted September 14, 2010.
Supported by the National Natural Science Foundation of China(Nos.20502017, 20872102).
504 CHEM. RES. CHINESE UNIVERSITIES Vol.27
([BMIM]·[CH3COO]) was prepared via the metathesis of round-bottom flask equipped with a reflux condenser and a
[BMIM]Cl and Ag+CH3COO–[17]. In a 50% aqueous MeOH magnetic stirrer in open air. In a typical reaction, 0.08 mmol of
solution, [BMIM]Cl and Ag+CH3COO– at a 1.1:1 molar ratio FeSO4 was dissolved in 5 mL of solvent consisting of
was mixed. After stirring at room temperature for 48 h, the [Et3NH][CH3COO] and glacial acetic acid with a volume ratio
precipitate was filtered off, and the water and MeOH were of 1:1(pH=3.4), then 1 mL(11.25 mmol) benzene and 1.2
removed by rotary evaporation. The crude IL was dissolved in mL(11.25 mmol) H2O2(30%, mass fraction) were added to the
CH2Cl2, and washed by cold water thoroughly until no Cl– was solution, and the solution was stirred at 60 ºC for 4 h under
detected by AgNO3 in water phase. The water phase was sepa- reflux.
rated by a separatory funnel, and the organic phase was evapo- After the reaction, the resulting mixture was extracted
rated under a vacuum to remove CH2Cl2. The product was with four portions of ether(20 mL). The extracts were dried,
dried at 80 ºC in high vacuum(666.61 Pa) for 2 h. The yield of and analyzed by Waters HPLC(ODS, 250 mm×4.5 mm, UV
[BMIM][CH3COO] was 75%. detector) with o-cresol as the internal standard. The mobile
1-n-Butyl-3-methylimidazolium nitrate([BMIM]NO3) was phase was the acetonitrile/water with a volume ratio of 1:1, and
synthesized via the metathesis of [BMIM]Cl and NH4NO3 in gradient elution was performed at a rate of 0.5 mL/min in the
acetone according to a published procedure[18]. The preparation first 3 min, then at 1.2 mL/min in the next 3 min, it was kept a
and purification procedures were the same as those of constant afterwards. Phenol, catechol, and hydroquinone were
[BMIM][CH3COO]. The yield of [BMIM][NO3] was 70%. detected at λ=225 nm, and benzoquinone was detected at
λ=254 nm. The yield and selectivity of phenol based on ben-
2.2 Hydroxylation Reaction zene, the yield of phenol based on H2O2, as well as the turnover
The hydroxylation reaction was carried out in a 50 mL number(TON) based on Fe were determined as follows:
Molar amount of phenol
Yield of phenol based on benzene(%, molar fraction)= ×100%
Molar amount of benzene initially added
Molar amount of phenol
Selectivity to phenol based on benzene(%)= ×100%
Total molar amounts of phenol, catechol,
hydroquinone, and benzoquinone
Molar amount of phenol
Yield of phenol based on H2O2(%)= ×100%
Molar amount of H2O2 initially added
Molar amount of phenol
Turnover number(TON) based on Fe=
Molar amount of FeSO4
aliphatic carboxylate anions coordinated to the Fe2+ ion, form-
3 Results and Discussion ing the Fe complexes. Thus a higher electrophilicity of the
Fe-complexes was deemed to be favorable for the interaction of
3.1 Effect of the Nature of Cations and Anions in H2O2 with the Fe center. In comparison, some common organic
ILs on the Hydroxylation solvents, such as ethanol, acetonitrile, and acetone were em-
Several hydrophilic ILs consisting of triethylammonium ployed as the solvents under the same reaction conditions. Only
cation and different anions(CH3COO–, C2H5COO–, C3H7COO–, trace amounts of phenol were obtained, while most of the cata-
NO3–, HSO4–, H2PO4–, ClO4–) were firstly synthesized, and lyst, FeSO4, remained un-dissolved even after the hydroxyla-
used as the solvents for a Fenton-like reaction. FeSO4, for its tion reaction.
low cost, was used as the catalyst. The solubilities of benzene Table 1 Solubility of benzene and hydroxylation
in these hydrophilic ILs were also measured and the results are activity in hydrophilic ILsa
shown in Table 1. It was found that benzene was miscible with Solubility of Yield of
TON based
Entry IL benzeneb / phenol
the ILs consisted of carboxylate anions, while the solubility on Fe
(g·mL–1) (%)
declined in the order of [Et3NH][NO3]>[Et3NH][ClO4]> 1 [Et3NH][CH3COO] Miscible 9.7 13.6
[Et3NH][HSO4], [Et3NH][H2PO4]. Correspondingly, the yield 2 [Et3NH][C2H5COO] Miscible 4.9 6.8
of phenol in these ILs was positively correlated with the solu- 3 [Et3NH][C3H7COO] Miscible 4.6 6.4
bility of the ILs. Higher phenol yield was obtained in 4 [Et3NH][NO3]c 0.58 10.0 14.0
[Et3NH][CH3COO] and [Et3NH][NO3]. However, there was 5 [Et3NH][HSO4]c 0.04 2.1 2.9
nitro-benzene produced in the latter IL, causing the decrease of 6 [Et3NH][H2PO4]c 0.05 1.6 2.2
selectivity in addition to over-oxidation. Thus, in the present 7 [Et3NH][ClO4]c 0.39 2.4 3.3
work, we focused on the use of [Et3NH][CH3COO] as the sol- 8 [BMIM][CH3COO] 0.10 Trace ―
vent. The hydroxylation activity decreased in the order of 9 [BMIM][NO3] 0.07 Trace ―
[Et3NH][CH3COO]>[Et3NH][C2H5COO]>[Et3NH][C3H7COO],
a. Reaction conditions: triethylammonium IL, 5 mL; FeSO4, 0.08 mmol;
contrary to the electron-donating ability of the anions. The benzene, 1 mL; H2O2(30%, mass fraction), 1.2 mL; 333 K; 4 h. b. Measured
UV-Vis spectra of the FeSO4-IL systems(Fig.1) reveal that the at 293 K. c. In solid state at room temperature.
No.3 HU Xiao-ke et al. 505
pH value was adjusted to below 3, the yield of phenol was lo-
wered to about 10% with only 0.25% of benzoquinone formed.
In such a case, there were no tars produced. The selectivity of
phenol based on benzene was improved to about 97.5% at a pH
value of 2. The lowest phenol yield of about 1% was obtained
in glacial acetic acid(pH=1.2) with no over-oxidation products.
The results reveal that the selectivity of phenol based on ben-
zene was improved by increasing the acidity of the system.
The effect of the acidity on the selectivity to phenol based
on H2O2 was also investigated by monitoring the amount of O2
evolved during the hydroxylation reaction in the [Et3NH]·
Fig.1 UV-Vis absorption spectra of FeSO4 in [Et3NH]X
[CH3COO] IL at different pH values. As shown in Table 2,
X–: a. CH3COO–; b. C2H5COO–; c. C3H7COO–.
Considering the higher activity of the catalyst in the trie- although the decomposition of H2O2 to O2 increased in more
thylammonium ILs with acetate and nitrate anions, two corres- acidic media, the selectivity to phenol based on H2O2 in the
ponding hydrophilic ILs based on 1-n-butyl-3-methylimidazo- hydroxylation was enhanced from 14% to 97%. That is, 97% of
lium cation([BMIM]) were prepared for comparison(Table 1, the un-decomposed H2O2 was used in the hydroxylation of
Entries 8, 9). However, only trace amounts of phenol were benzene to phenol at a pH value of 2. On account that benzene
produced in [BMIM][CH3COO] and [BMIM][NO3]. Sub- could be recycled but H2O2 could not, the enhancement of the
stances such as N-butyl-formamide and 1-butyl-3-methyl-2, 4, selectivity to phenol based on H2O2 was of more importance.
5-trioxoimidazolidine, originated from the degradation of Thus a [Et3NH][CH3COO] IL medium with pH range between
BMIM cation, were detected by GC-MS. The result was con- 2 and 3 was more favorable for obtaining a higher selectivity to
sistent with the literature dealing with the effective degradation phenol based on H2O2.
of 1-butyl-3-methylimidazolium in a Fe3+/H2O2 system[19]. So a Table 2 Decomposition of H2O2 to dioxygen during
hydrophilic IL consisted of [Et3NH] cation was more suitable the hydroxylation reaction in [Et 3 NH]·
than commonly used [BMIM] cation as the Fenton-like reac- [CH3COO] at different pH valuesa
Conversion of Yield of phenol based Selectivity to phenol
tion medium for the target reaction. Entry pH
H2O2b(%) on H2O2(%) based on H2O2c(%)
1 6.4 52 7.4 14
3.2 Effect of the Acidity in [Et3NH][CH3COO] IL 2 4.7 49 14.2 30
on the Selectivity to Phenol 3 3.4 39 17.0 45
4 2.7 32 16.5 52
The medium of [Et3NH][CH3COO] was near neutral with
5 2.4 19 15.9 82
a pH value equal to 6.4. The hydroxylation reaction carried out 6 2.0 15 14.8 97
in this medium gave a phenol yield of 9.7% based on benzene, a. Reaction conditions: VIL+VAcOH =10 mL; FeSO4, 0.08 mmol; ben-
with small amounts of catechol, hydroquinone and benzoqui- zene, 11.25 mmol; H2O2(30%, mass fraction), 1.76 mmol; 333 K; 4 h. b.
none formed. Tars were observed according to the color varia- Conversion of H2O2(%) =(initial amount of H2O2 –decomposed amount of
H2O2)/initial amount of H2O2×100%. c. Selectivity to phenol based on
tion of the reaction mixture from orange to black. The medium
H2O2(%)=amount of phenol/(initial amount of H2O2 – decomposed amount
was then adjusted to be acidic by mixing [Et3NH][CH3COO] of H2O2) ×100%.
and acetic acid with different volume ratios. As indicated in
Fig.2, in the pH value range of 3―4 was found most favorable 3.3 Efficiency of H2O2 in [Et3NH][CH3COO] IL
for the enhancement of the phenol yield up to 12%, but Tars for the Hydroxylation
still formed, with trace amounts of catechol, hydroquinone and
benzoquinone produced(total yield of about 0.8%). When the The efficiency of H2O2 is a major problem for the direct
production of phenol from benzene and hydrogen peroxide.
The low efficiency always generates from the un-productive
decomposition of H2O2 and the further-oxidation of the pro-
duced phenol. To partly solve this problem, an excessive
amount of benzene was used. As indicated in Fig.3, as the mo-
lar ratio of benzene to H2O2 was elevated from 2:1 to 10:1, the
absolute amount of phenol produced increased and the yield of
phenol based on H2O2 augmented from 15.5% to 21%. The
only by-product was trace amount of benzoquinone, and its
amount successively decreased with increasing the amount of
benzene. Notably, when the molar ratio of benzene to H2O2
Fig.2 Effect of the pH values on the yield of the exceeded 6, while 5 mL solvent remained constant, a ben-
products based on benzene zene-IL bi-phase system was observed. Although the
■ Phenol; ● hydroquinone; ▲ catechol; ▼ benzoquinone. Reaction condi-
above-mentioned experiment showed remarkable solubility of
tions: VIL+VAcOH=5 mL; FeSO4, 0.08 mmol; benzene, 1 mL; H2O2(30%,
mass fraction), 1.2 mL; 333 K; 4 h. benzene in the [Et3NH][CH3COO] IL, the addition of water
506 CHEM. RES. CHINESE UNIVERSITIES Vol.27
[1, 20]
contained in the aqueous H2O2(30%, mass fraction) surely de- the traditional Fenton chemistry . However, in the present
creased the solubility. It was found that the catalyst still existed acidic [Et3NH][CH3COO] system, TON could be greatly en-
in the IL phase, while most of phenol was dissolved in benzene hanced to 25 when the molar ratio of Fe2+/H2O2 was 1:280.
layer. Because phenol formed was transferred to benzene layer, Furthermore, it was proved that the TON was further enhanced
the contact of phenol with the catalyst and oxidant was directly to 120 in the benzene-IL bi-phase system, comparable to that of
avoided. The selectivity to phenol based on benzene was en- the Fe-complexes mimicking cytochromes P450 with N-S do-
hanced to above 99.5% in such a benzene-IL bi-phase system. nor[21] or the no-heme monoxygenase system[22]. The distinct
Furthermore, in comparison with the yield of 17% based on improvement of TON in the [Et3NH][CH3COO] system meant
H2O2 obtained in a homogeneous system(pH=3.4, at a molar much higher catalytic efficiency was attained.
ratio of benzene to H2O2 of 6:1 in Table 2, Entry 3), the yield After the products were extracted by ether, the IL with the
increased to 20% in this bi-phase system. Thus it is deduced catalyst was reused for the next cycle without any recovery
that the efficiency of H2O2 and selectivity of the hydroxylation treatment. Under the identical reaction conditions, the yield of
reaction are both improved by the hydrophilic IL-benzene bi- phenol remained about 10% after four cycles which indicated
phasic system. that the hydroxylation activity remained relatively stable. The
IR spectra of the initial [Et3NH][CH3COO] and that after four
times of usage are presented in Fig.4. The characteristic bands
for tert-ammonium salts at 2596, 2491 and 1263 cm–1, and the
bands at 1563 and 1399 cm–1 ascribed to C=O stretching vi-
bration for acetate anion still remained after reaction. Further
more, there was no other new band appeared. The IR spectra
indicate that the structure of the IL remained stable during the
hydroxylation.

Fig.3 Effect of molar ratio of benzene to

H2O2 on efficiency of H2O2
■ Selectivity to phenol; ▲ yield of phenol based on benzene; ▼ yield of
phenol based on H2O2. Reaction conditions: VIL+VAcOH=5 mL, pH=3.4;
FeSO4, 0.08 mmol; H2O2(30%, mass fraction), 0.6 mL; 333 K; 4 h.
The efficiency of H2O2 on the formation of phenol in the
[Et3NH][CH3COO] IL was 20%―25% with a relatively larger
molar ratio of H2O2 to Fe(70:1). It is well known that the higher
concentration of H2O2 will induce its fast decomposition to O2,
Fig.4 FTIR spectra of [Et3NH][CH3COO]
lowering the efficiency of H2O2 for the hydroxylation. A con-
a. Before reaction; b. after four times of reactions.
trol experiment on the decomposition of H2O2 catalyzed by
FeSO4 in water or [Et3NH][CH3COO] system in the absence of 4 Conclusions
benzene was carried out by titrating the residual H2O2 with
aqueous potassium permanganate at 60 ºC. It was found that When a Fenton-like system in a medium of hydrophilic IL
H2O2 still remained in [Et3NH] [CH3COO] after 30 min, while was applied to the hydroxylation of benzene to phenol, the
no H2O2 was left in water only within 5 min. The result indi- solubility of benzene was proved to be an important factor. In
cates that the decomposition of H2O2 catalyzed by FeSO4 was an optimized hydrophilic IL, [Et3NH][CH3COO], the acidity of
retarded in medium [Et3NH][CH3COO]. the medium was proved to be crucial for the reaction. Com-
In addition, the control experiments on the oxidation of pared with that of H2O2 in the aqueous Fenton system at the
phenol by H2O2 in water or [Et3NH][CH3COO] system were similar pH, the decomposition of H2O2 was retarded, and
then comparatively carried out. Under the identical reaction over-oxidation was effectively reduced in the [Et 3 NH]·
conditions, no matter in the presence or absence of the catalyst, [CH3COO] IL. The selectivity of phenol, the utilization of
much more amounts of phenol were converted to over- H2O2, as well as the TON of the catalyst were enhanced in a
oxidation products in water than that in [Et3NH][CH3COO] IL. benzene-[Et3NH][CH3COO] bi-phase system. Significantly, the
As phenol was taken as an intermediate for the over-oxidation catalyst together with [Et3NH][CH3COO] IL could be recycled
in the hydroxylation of benzene, over-oxidation was restrained with stable catalytic performance.
in [Et3NH][CH3COO] IL compared with that in the traditional
aqueous Fenton system. References
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