Selective cyclohexane oxidation catalyzed by manganese porphyrins and co-catalysts

Article abstract of DOI:10.1016/j.cattod.2015.07.034

Several polar molecules, such as alcohols, ketones, esters and acids, were used as co-catalysts for the cyclohexane oxidation catalyzed by manganese porphyrins, and the catalytic activity was found to be closely related to polarity of co-catalysts. The results indicated that the total selectivity of products was as high as 96.3% and glutaric acid selectivity was up to 50.9%. Thus, the proposed method provides a new approach for preparing glutaric acid.

Full text of DOI:10.1016/j.cattod.2015.07.034

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Selective cyclohexane oxidation catalyzed by manganese porphyrins
and co-catalysts
a
b,a,∗
c,∗∗
, Hui Lia
Tao Wang , Yuanbin She
, Haiyan Fu
a
Institute of Green Chemistry and Fine Chemicals, College of Environmental & Energy Engineering, Beijing University of Technology, Beijing, 100124, China
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014, China
College of Pharmacy, South-Central University for Nationalities, Wuhan, 430074, China
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
Several polar molecules, such as alcohols, ketones, esters and acids, were used as co-catalysts for the
cyclohexane oxidation catalyzed by manganese porphyrins, and the catalytic activity was found to be
closely related to polarity of co-catalysts. The results indicated that the total selectivity of products was
as high as 96.3% and glutaric acid selectivity was up to 50.9%. Thus, the proposed method provides a new
approach for preparing glutaric acid.
Received 12 May 2015
Received in revised form 13 July 2015
Accepted 15 July 2015
Available online xxx
©
2015 Elsevier B.V. All rights reserved.
Keywords:
Cyclohexane
Selective oxidation
Manganese porphyrins
Co-catalysts
Organic acids
1
. Introduction
bond-breaking. Increases in solvent polarity gradually increase the
beta-bond breaking ability of epoxy radicals. Sheldon et al. [14]
observed the same phenomenon during catalytic cyclododecane
oxidation. While no acids were generated when benzotrifluoride
was used as a solvent, acetic acid exerted opposite effects. Hermans
and Peeters et al. [15,16] reported that cyclohexanone presents
good effects on cyclohexane oxidation, as verified by experimental
and computational methods. Weng et al. [17,18] studied the
liquid-phase cooxidation of cyclohexane and cyclohexanone, and
proposed possible routes to obtain glutaric and succinic acids.
Ishii et al. [19] reported the cyclohexane oxidation in air under
mild condition without the use of any solvent by employing the
lipophilic NHPI derivatives, which are easily dissolved in alkanes.
Simonato et al. [20] reported one-step process for obtaining adipic
acid from cyclohexane using a very stable lipophilic carboxylic
acid and very low manganese and cobalt salts loadings. This new
approach to produce adipic acid avoids the final nitric oxidation
step, which generates a strong greenhouse gas, and thus provides
an environmentally benign alternative to an important industrial
reaction. Miyake et al. [9] reported the cyclohexane oxidation
with molecular oxygen using a novel system composed of isoamyl
Cyclohexane is an important hydrocarbon and bulk chemicals
[
1]. The oxidation products of cyclohexane include cyclohexanol,
cyclohexanone, adipic acid, and glutaric acid etc. Selective cyclo-
hexane oxidation is a significant process in the chemical industry
because the products of this reaction may be utilized in a number of
ways [2–4]. Cyclohexanol and cyclohexanone are valuable chemi-
cal intermediates for preparing adipic acid and caprolactam [5–8].
Adipic acid is an important intermediate used for manufacturing
nylon-6,6 and nylon-6 polymers, urethane foams, plasticizers, and
lubricants etc. [9–12]. Therefore, the direct oxidation of cyclohex-
ane into adipic acid under mild reaction conditions is a worthwhile
endeavor.
The generation of dicarboxylic acids was considered in two
approaches: cyclohexanone oxidation and beta bond-breaking of
epoxy radicals. Lusztyk et al. [13] reported that the solvents exert
an important effect on epoxy radical dehydrogenation and beta
∗
Corresponding author at: College of Chemical Engineering, Zhejiang
nitrite, Co(acac)3 and Mn(acac) . In this reaction, the nitrite con-
3
University of Technology, Hangzhou 310014, China. Tel.: +86 0571 88320533;
fax: +86 0571 88320533.
∗
tributed to the rate-determining step, which involves the initial
dissociation of C–H bond of cyclohexane, and the Co and Mn
promoters contributed to the succeeding oxidation steps; a high
adipic acid selectivity of about 40% was also attained. Xu et al. [21]
∗ Corresponding author. Tel.: +86 027 67843352; fax: +86 027 67843352.
E-mail addresses: sheyb@zjut.edu.cn (Y. She), fuhaiyan@mail.scuec.edu.cn
(
H. Fu).
http://dx.doi.org/10.1016/j.cattod.2015.07.034
920-5861/© 2015 Elsevier B.V. All rights reserved.
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2
reported the hydrocarbons oxidation catalyzed by a MgCl /NHPI
and GC/MS; here, 2-ethylhexanoic acid was used as an internal
standard [38].
2
system and found that MgCl2 remarkably promotes effect on
NHPI-catalyzed aerobic oxidation of cyclohexane. Li et al [22]
investigated the cyclohexane oxidation catalyzed by several small
organic molecules including ketones, aldehydes, esters, alcohols
and amines. The catalytic activity was found to be closely related
to polarity, ␣-H activity, the strength of the hydrogen bond formed
with cyclohexane and the radical scavenging capability of these
3. Results and discussion
.1. Cyclohexane oxidation catalyzed by [MnIIIT(p-Cl)PP]Cl and
3
co-catalysts
molecules. Hwang et al [11] reported a N O-free process for adipic
2
First, the aerobic oxidation of cyclohexane with O catalyzed
2
acid synthesis. Treatment of neat cyclohexane, cyclohexanol,
or cyclohexanone with ozone at room temperature and 1 atm
affords adipic acid as a solid precipitate. Zhong and Lin et al. [23]
reported one-step oxidation of cyclohexane into adipic acid over
manganese-doped titanium silicalite with hollow structure (HTS)
using oxygen as oxidant without any initiator or solvent. Here,
the catalyst exhibited high conversion (13.4%) and reasonable
adipic acid selectivity (57.5%). Bal et al. [24] prepared a CuCr O
III
by [Mn T(p-Cl)PP]Cl and co-catalysts was investigated, and the
relevant results are summarized in Table 1. The main oxidation
products (Scheme 1) were adipic acid (AA, 1), cyclohexanol (2), and
cyclohexanone (3).
Table 1 shows that the cyclohexane oxidation without co-
catalysts hardly occurs (Entry 1). The same observation holds
true for oxidation of cyclopentanol and cyclooctanol (Entries 2–3),
which present fairly low polarity. The reaction was achieved and
showed good effects with cycloalkanones (Entries 4–7). Molecu-
lar polarity decreased with increasing number of cycloalkanone
rings, and total selectivity decreased. Cycloalkanones were utilized
completely during the reaction. Thus, they could not be recov-
ered as catalyst. Considering these results, cycloalkanones were not
taken into account in subsequent studies. N-Hydroxyphthalimide
2
4
spinel nanoparticle catalyst that was speculated to be highly active
for selective oxidation of cyclohexane into cyclohexanone with
H O . A cyclohexane conversion rate of 70% and cyclohexanone
2
2
◦
selectivity of 85% was achieved at 50 C.
In conclusion, there were some disadvantages in the above
methods of cyclohexane oxidation. For example, reaction condi-
tions were harsh and use of solvent, reaction system was complex,
and catalyst was difficult to prepare. Therefore, the cost of cyclo-
hexane oxidation was high.
Metalloporphyrins have recently been recognized as valuable
biomimetic catalysts for oxidation of hydrocarbons because of their
high selectivity and efficiency [12,25–32], in particular, cyclohex-
ane oxidation with metalloporphyrins has been extensively studied
(
NHPI) and N,N-Dimethylformamide (DMF) (Entries 13–14), which
present high polarity, showed fairly extensive cyclohexane con-
version. Product selectivity was very low because of the increased
occurrence of side reactions. Cyclohexane conversion and prod-
uct selectivity increased when organic acids, namely acetic acid
(
CH COOH) and benzoic acid (PhCOOH), were reacted. Benzoic acid
3
also showed good effects on the catalytic reaction.
[
33,34]. The direct aerobic oxidation of cyclohexane into adipic acid
According to the reported literatures and our experimental
phenomena, the oxidation of cyclohexane was a free radical reac-
tion. Firstly, high-valence porphyrin intermediates captured ␣-H
III
catalyzed by Fe T(o-Cl)PP was firstly reported by our group; in this
method, molecular oxygen was used as an oxidant without any
solvents and promoters [33].
•
•
from cyclohexane to form the free radical R . Then R trapped O to
2
In this present paper, we employed co-catalysts during the
selective oxidation of cyclohexane catalyzed by manganese por-
phyrins to increase product selectivity.
generated peroxide free radicals which could initiate crossly more
free radicals from cyclohexane. The rapidly increase of free radical
concentration promoted the propagation of free-radical reactions.
The oxidation of cyclohexane produced ROOH as the intermediates
which could be immediately decomposed to ketone and alcohol
by manganese porphyrins. Meanwhile, this reaction also produced
2
. Experimental
•
RO which could react with cyclohexane and ring-open via ␤ C–C
2.1. Instruments and reagents
cleavage. These radicals were further oxidized to produce AA and
other decarboxylated by-products.
Preliminary materials purchased from commercial sources were
From the above results we could know that the polarity of co-
catalysts was important for the cyclohexane oxidation catalyzed by
manganese porphyrins. Because of the addition of co-catalyst, such
as PhCOOH, the a-H was more easily to be captured from cyclohex-
ane at lower temperature. Thus, the conversion rate of cyclohexane
was increased.
of analytical grade and used without further treatment unless indi-
cated. The metalloporphyrins catalysts were prepared according
to previously published procedures [35–37], and their structures
were characterized by UV–vis, IR, and elementary analysis.
2
.2. General procedures for cyclohexane oxidation
3
.2. Cyclohexane oxidation with dioxygen catalyzed by
III
[Mn T(p-Cl)PP]Cl and PhCOOH
The cyclohexane oxidation with oxygen as an oxidant catalyzed
by manganese porphyrins and co-catalysts was conducted as fol-
lows: Cyclohexane, manganese porphyrins and co-catalysts were
charged into a 100 mL autoclave equipped with an electromag-
netic stirrer and a temperature-controlling device. The mixture
was heated to 3 C below the set value (120/140 C). The reactor
was then charged with O2 once, or the reaction system pressure
was maintained at the set value. The mixture was stirred with the
stirring rate of 800 rpm for certain time. The reactor was cooled
to room temperature and the mixture was dissolve with acetone
after completion of the reaction. The remaining reactants were ana-
lyzed by GC (Agilent HP-5MS) with methylbenzene as an internal
standard. The oxidized products were derived through silylation
The aerobic oxidation of cyclohexane with O2 catalyzed by
Mn T(p-Cl)PP]Cl and PhCOOH was subsequently investigated. The
main oxidation products (Scheme 2) were adipic acid (AA, 1), cyclo-
hexanol (2), cyclohexanone (3) and glutaric acid (GA, 4).
III
[
◦
◦
3
.2.1. Effect of benzoic acid amounts on cyclohexane oxidation
The results in Table 2 reveal that cyclohexane conversion grad-
ually increases with increasing PhCOOH content. The system with
mol% PhCOOH performed well during the reaction. Product yield
increased with further increases in PhCOOH content, but the selec-
tivity gradually decreased. Therefore, the appropriate PhCOOH
dosage is 5 mol%.
5
(
BSTFA: TMCS = 99:1) and monitored through GC (Agilent HP-5ms)
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Table 1
Cyclohexane oxidation catalyzed by [MnIIIT(p-Cl)PP]Cl and co-catalysts.a
Entry
Co-catalysts
Conversion [%]
Yield [%]
1
Selectivity [%]
2
3
Total
1
2
3
Total
1
2
Blank
N.R.
N.R.
Cyclopentanol
3
N.R.
Cyclooctanol
4
5
12.4
13.6
3.9
3.6
3.1
3.2
3.9
3.8
10.9
10.6
31.5
26.5
25.0
23.5
31.5
27.9
88.0
77.9
Cyclopentanone
4
-Methylcyclohexanone
6
7
12.7
13.1
3.0
2.5
3.1
3.2
3.9
4.0
10.0
9.7
23.6
19.1
24.4
24.4
30.7
30.5
78.7
74.0
Cycloheptanone
Cyclooctanone
8
9
6.6
3.2
1.4
1.2
5.8
48.5
21.2
18.2
87.9
NMP, 1-Methyl-2-pyrrolidinone
ε-Caprolactone
N.R.
1
1
1
0
1
2
N.R.
5.9
Acetophenone
DMSO
1.6
1
–
–
27.1
18.9
–
–
5.3
1.3
1.4
3.7
3.6
24.5
26.4
69.8
30.0
Cyclohexene
13
14
15
NHPI
DMF
DMA
12.0
27.6
N.R.
0.9
0.6
0.7
–
2.0
–
7.5
2.2
5.8
–
16.7
–
1
6
N.R.
Isopropylbenzene
1
1
7
8
CH3COOH
PhCOOH
9.6
14.2
2.4
2.4
2.4
1.2
2.5
4.1
7.3
7.7
25.0
16.9
25.0
8.5
26.0
28.9
76.0
54.3
a
Reaction conditions: [MnIIIT(p-Cl)PP]Cl (7 × 10−4 mol%), co-catalyst (30 mol%), 120 C, O2 pressure 1.4 MPa (continuous) for 3 h, 800 rpm.
◦
3
.2.2. Effect of reaction pressure on cyclohexane oxidation
The results listed in Table 3 demonstrate that oxygen pressure
selectivity did not increase significantly. Thus, in subsequent exper-
iments, an oxygen pressure of 2.5 MPa was adopted.
exerts a certain influence on cyclohexane oxidation. Cyclohexane
conversion increased when the oxygen was sustained by 1.4 MPa.
When the oxygen pressure was charged once, reaction conver-
sion increased as the initial oxygen pressure increased. However,
3.2.3. Effect of different catalysts on cyclohexane oxidation
The results in Table 4 reveal that the reaction is influenced by
III
the type of manganese porphyrins applied. Mn T(p-Cl)PP showed
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Scheme 1. Cyclohexane oxidation with dioxygen catalyzed by [MnIIIT(p-Cl)PP]Cl and co-catalysts.
Table 2
a
Effect of PhCOOH amount on cyclohexane oxidation .
Entry
PhCOOH amount [mol%]
Conversion [%]
Yield [%]
1
Selectivity [%]
2
3
4
Total
1
2
3
4
Total
1
2
3
4
0
5
10
15
12.9
23.6
29.3
39.3
1.7
6.3
9.1
2.1
1.7
2.1
2.4
3.1
5.0
5.4
6.4
1.1
5.8
5.1
5.1
8.0
18.8
21.7
24.9
13.2
26.7
31.1
28.0
16.3
7.2
7.2
24.0
21.2
18.4
16.3
8.5
62.0
79.7
74.1
63.4
24.6
17.4
13.0
11.0
6.1
a
Reaction conditions: [MnIIIT(p-Cl)PP]Cl (7 × 10−4 mol%), 140 C, O2 pressure 1.4 MPa (continuous) for 3 h, 800 rpm.
◦
Scheme 2. Cyclohexane oxidation with dioxygen catalyzed by [MnIIIT(p-Cl)PP]Cl and PhCOOH.
Table 3
Effect of reaction pressure on cyclohexane oxidation.
a
Entry
Pressure [MPa]
Conversion [%]
Yield [%]
1
Selectivity [%]
2
3
4
Total
1
2
3
4
Total
b
1
2
3
1.4
23.6
19.3
20.7
6.3
6.4
7.1
1.7
2.3
2.0
5.0
4.7
5.2
5.8
3.2
3.4
18.8
16.6
17.7
26.7
33.2
34.3
7.2
11.9
9.7
21.2
24.4
25.1
24.6
16.6
16.4
79.7
86.0
85.5
c
2.5
c
3.0
a
Reaction conditions: [MnIIIT(p-Cl)PP]Cl (7 × 10−4 mol%), PhCOOH (5 mol%),140 C for 3 h, 800 rpm.
◦
b
c
O2 pressure 1.4 MPa (continuous).
Initial O2 pressure (one time).
Table 4
a
Effect of manganese porphyrins on cyclohexane oxidation.
Entry
Manganese porphyrins
Conversion [%]
Yield [%]
1
Selectivity [%]
2
3
4
Total
1
2
3
4
Total
1 + 4
III
1
2
3
4
5
[Mn T(p-Cl)PP]Cl
19.3
20.0
16.4
17.1
16.4
6.4
4.8
5.3
5.9
6.3
2.3
2.0
2.0
2.0
2.0
4.7
4.4
4.5
4.4
4.5
3.2
4.8
3.6
2.9
3.0
16.6
16.0
15.4
15.2
15.8
33.2
24.0
32.3
34.5
38.4
11.9
10.0
12.2
11.7
12.2
24.4
22.0
27.4
25.7
27.4
16.6
86.0
80.0
93.9
88.9
96.3
49.7
48.0
54.3
51.5
56.7
III
[Mn T(p-OCH3)PP]Cl
24.0
22.0
17.0
18.3
III
[Mn T(p-NO2)PP]Cl
III
[Mn T(o-Cl)PP]Cl
III
Mn T(p-Cl)PP
a
Reaction conditions: [MnIIIT(p-Cl)PP]Cl (7 × 10−4 mol%), PhCOOH (5 mol%), 140 C for 3 h, initial O2 pressure 2.5 MPa, 800 rpm.
◦
good results with a total selectivity of products up to 96.3%, and the
total selectivity of adipic acid and glutaric acid up to 56.7%.
The results in Table 5 reveal that organic acids exert an impor-
tant influence on the conversion reaction. Cyclohexane conversion
gradually decreased among the substituted benzoic acids (Entries
1
–5). Benzoic acid showed better effects than other acids. A yield
3.3. Cyclohexane oxidation catalyzed by manganese porphyrins
and selectivity of 6.3% and 38.4%, respectively, were obtained with
benzoic acid, and total product selectivity was as high as 96.3%.
The use of dicarboxylic acids (Entries 6–9) caused gradual
decreases in the total selectivity of adipic acid and glutaric acid.
As malonic acid is broken down at 140 C, the reaction tempera-
ture was not excessively high. With the conditions of malonic acid
and organic acids
The aerobic oxidation of cyclohexane with O2 catalyzed by
III
Mn T(p-Cl)PP and organic acids was investigated. The main oxi-
◦
dation products (Scheme 3) were adipic acid (AA, 1), cyclohexanol
(
2), cyclohexanone (3) and glutaric acid (GA, 4).
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OH
2
O
3
III
Mn T(p-Cl)PP, Organic acid
COOH
+
+
HOOC
O , T, P
2
1
+ HOOC
+ by-products
COOH
4
Scheme 3. Oxidation of cyclohexane with dioxygen catalyzed by MnIIIT(p-Cl)PP and organic acids.
Table 5
a
Cyclohexane oxidation catalyzed by manganese porphyrins and organic acids.
Entry
Organic acids
Conversion [%]
Yield [%]
1
Selectivity [%]
2
3
4
Total
1
2
3
4
Total
1 + 4
1
2
3
4
5
(p-tBu)PhCOOH
(p-Cl)PhCOOH
PhCOOH
(p-C2H5)PhCOOH
(p-OMe)PhCOOH
Malonic acid
Succinic Acid
Glutaric acid
Adipic acid
Isonicotinic acid
Acetic acid
Pentanoic acid
Hexanoic acid
21.9
20.0
16.4
14.3
7.1
5.7
10.0
9.0
3.9
5.5
6.3
4.5
2.2
1.8
3.4
2.0
0.9
1.1
3.5
6.0
5.7
2.2
2.6
2.0
2.1
1.2
0.0
1.2
1.2
0.7
2.1
1.6
2.6
2.4
5.5
5.0
4.5
3.8
1.2
0.0
2.1
1.3
1.4
2.5
4.1
5.7
4.9
4.4
0.0
3.0
2.0
0.0
2.9
2.9
2.2
2.9
3.4
4.9
2.4
2.1
16.0
13.1
15.8
12.4
4.6
4.7
9.6
6.7
5.9
17.8
27.5
38.4
31.5
31.0
31.6
34.0
22.1
10.5
7.3
10.0
13.0
12.2
14.7
16.9
0.0
12.0
13.3
8.1
14.0
10.2
14.5
12.4
25.1
25.0
27.4
26.6
16.9
0.0
21.0
14.5
16.3
16.7
26.1
31.8
25.4
20.1
0.0
18.3
14.0
0.0
50.9
29.0
24.5
33.7
22.7
31.2
13.4
10.9
73.1
65.5
96.3
86.7
64.8
82.5
96.0
74.4
68.6
60.7
89.8
93.3
78.2
37.9
27.5
56.7
45.5
31.0
82.5
63.0
46.6
44.2
30.0
53.5
46.9
40.4
b
6
7
8
9
0
1
2
3
8.6
1
1
1
1
15.0
15.7
17.9
19.3
9.1
14.1
16.7
15.1
22.3
33.5
29.5
a
Reaction conditions: organic acids (5 mol%), MnIIIT(p-Cl)PP (7 × 10−4 mol%), 140 C for 3 h, initial O2 pressure 2.5 MPa, 800 rpm.
◦
b
◦
1
20 C.
III
−4
◦
(
5 mol%), Mn T(p-Cl)PP (7 × 10 mol%), 120 C for 3 h, initial O2
pressure 2.5 MPa, and 800 rpm, glutaric acid selectivity reached
0.9% and the total selectivity of adipic acid and glutaric acid were
Acknowledgments
5
This work was supported by the State Key Program, General
and Youth Projects of National Natural Science of China (Grant
Nos. 21036009, 21476270, 21276006, 21076004, 21205145) and
the Open Funds of State Key Laboratory Breeding Base of Green
Chemistry-Synthesis Technology of Zhejiang University of Tech-
nology (No. GCTKF2014003, GCTKF2014007).
as high as 82.5%. These results demonstrate that the proposed
method provides a new approach for preparing glutaric acid.
4
. Conclusions
References
In summary, several polar molecules such as alcohols, ketones,
esters, and acids were used as co-catalysts for the cyclohexane oxi-
dation catalyzed by manganese porphyrins. The results indicated
that the catalytic activity was closely related to polarity.
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Catal. Today (2015), http://dx.doi.org/10.1016/j.cattod.2015.07.034

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