Direct cyclohexanone oxime synthesis: Via oxidation-oximization of cyclohexane with ammonium acetate

Article abstract of DOI:10.1039/c9cc09840b

An unexpected cascade reaction for oxidation-oximization of cyclohexane with ammonium acetate was developed for the first time to access cyclohexanone oxime with 50.7% selectivity (13.6% conversion). Tetrahedral Ti sites in Ni-containing hollow titanium silicalite can serve as bifunctional catalytic centers in the reaction. This methodology not only provides a direct approach to prepare cyclohexanone oxime, but also simplifies process chemistry. Various available nitrogen sources, such as ammonium salt and even ammonia can be used as starting materials.

Full text of DOI:10.1039/c9cc09840b

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DOI: 10.1039/C9CC09840B
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Direct cyclohexanone oxime synthesis via oxidation-oximization
of cyclohexane with ammonium acetate
Ling Peng,a Chan Liu,a Na Li,a Wenzhou Zhong,*a Liqiu Mao,*a Steven Robert Kirka and Dulin Yina
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
An unexpected cascade reaction for oxidation-oximization of consumptions. Recently, it was reported that, with
cyclohexane with ammonium acetate was developed for the first improvements in efficiency, such a direct ammoximation of
4
time to access cyclohexanone oxime with 50.7% selectivity (13.6% cyclohexanone
with
NH3
or
hydrogenation
of
conversion). Tetrahedral Ti sites in Ni-containing hollow titanium nitrocyclohexane (or nitrobenzene)5 to cyclohexanone oxime
silicalite can serve as bifunctional catalytic centers in the reaction. (Scheme S1) can be less expensive than the existing multistep
This methodology not only provides a direct approach to prepare processes.
A
direct photochemical transformation of
cyclohexanone oxime, but also simplifies process chemistry. cyclohexane into cyclohexanone oxime using t-butyl nitrite and
Various available nitrogen sources, such as ammonium salt and UV-LED diodes is also described.6 To our knowledge, however,
even ammonia can be used as starting materials.
no reaction has yet been developed where cyclohexanone
oxime is directly accessible from cyclohexane and ammonium
salt or NH3 in a single catalytic system.
The catalytic functionalization of hydrocarbons from
petroleum is one of the greatest challenges that must be met
for inert sp3 C–H bond activation to be used widely in organic
synthesis.1 Cyclohexanone oxime is an important chemical
intermediate for the manufacture of nylon-6, 6. Most
industrial processes of cyclohexanone oxime production
involve multiple steps:2 (a) aerobic oxidation of cyclohexane to
a mixture of cyclohexanol and cyclohexanone (KA oils), (b)
conversion of ammonia to NH2OH salts, (c) and finally
oximization of cyclohexanone with NH2OH salts (Scheme S1).
In this process, the aerobic oxidation of cyclohexane suffers
from the low conversion of less than 5% by preventing the
deep-oxidation of KA oils and also involves the generation of
alkaline waste. In addition, the preparation of NH2OH salts
requires strongly acidic conditions and precious metal catalysts
for catalytic reduction of nitrate salts or nitric oxide derived
from NH3, and the oximization process coproduces large
volumes of inorganic salt waste. Research efforts are being
directed at more direct methods to produce cyclohexanone
oxime, such as the ultraviolet photonitrosation of cyclohexane
using NOCl or the nitrosation of cyclohexane with NOHSO4 in
fuming H2SO4 medium,3 but these processes involve highly
corrosive nitrosating reagents and/or high energy
Titanium-silicalite (TS-1), with MFI cages connected by 10-
ring pore openings, has been known for its remarkable
catalytic activity in alkane oxidation,7 alkene epoxidation,8
cyclohexanone ammoxidation9 and phenol hydroxylation.10
The isolated Ti-O4 species in the silicate frameworks have been
hypothesized to be critical active sites for activation of H2O2.
The microporous structure of the TS-1 zeolite core, more
specifically its bidirectional micropore (0.55 nm), however,
strongly hinders the diffusion of reactants to the Ti-O4 sites
and thus constrains its catalytic activity. The preparation of
hollow-structured TS-1 (HTS) is therefore carried out today by
using post-treatment desilication, and the formation of the
intra-particle pores in the structure can intensify the diffusion
and accessibility to Ti-O4 sites.11 Accordingly, HTS is shown to
be more active than solid-structured TS-1. Meanwhile, results
from the current study demonstrates that by modifying the
electronic structure of Ti-O4 sites in TS-1 the product selectivity
can be tuned. Au-modified TS-1 was reported to achieve high
propylene oxide selectivity in direct propene epoxidation with
H2 and O2.12 B-doped TS-1 used in the presence of a particular
sulfolane co-solvent is capable of protecting the produced
phenol from over-oxidation and dramatically enhanced the
reaction selectivity.13 Recent studies from our laboratory have
shown that the TS-1 implanted with transition metal Mn(IV)
ions is more adapted for the production of adipic acid
compared with KA-oil.14 Therefore, designing an efficient TS-1
catalyst with prominently improved catalytic activity and
product selectivity is of prime scientific and industrial
importance.
a. National & Local United Engineering Laboratory for New Petrochemical Materials
& Fine Utilization of Resources, Key Laboratory of Chemical Biology Traditional
Chinese Medicine Research Ministry of Education, College of Chemistry and
Chemical Engineering, Hunan Normal University, Changsha 410081, PR China.
E-mail: zwenz79@163.com (W. Zhou); mlq1010@126.com (L. Mao).
†Electronic Supplementary Information (ESI) available: experimental details and
catalysis results. See DOI: 10.1039/x0xx00000x
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We herein describe a direct, one-step approach to construct the introduction of Ni species and influences the local chemical
View Article Online
cyclohexanone oxime enabled by a modified hollow TS-1 state of Ti4+ ions. The BE of Ni 2p3/2 at 855.0 eV22
DOI: 10.1039/iCn9CNCi/0H9T84S0iBs
catalyst using 30% H2O2 as the oxidant in a suitable solvent. lower than that in Ni/silicalite-1 (856.1 eV), which indicates
This one-pot strategy uses cyclohexane and ammonium salt that the Ni species in Ni/HTS have a partial positive charge
( or NH3) as readily available starting materials (Scheme 1), (Niδ+) due to the electron transfer between the Ti4+ and Ni2+
which simplifies process chemistry and obviates energy in ions.
intermediary isolation. The key element for success in this
tandem reaction is a catalyst-directed selective oxidation of
different reactants with in-situ generation of cyclohexanone
and NH2OH intermediates, as an alternative to the oximization
leading to cyclohexanone oxime.
B
A
A
B
Fig. 2 N2 adsorption-desorption (A) and UV-vis (B)
Based on the above experimental studies, the structural
modification of HTS by the introduction of Ni atom is further
studied by DFT calculation. Fig.S4 shows that three of the Ti–O
bond lengths of framework Ti sites in Ni/HTS are found to be
lengthened to 1.804–1.817 Å from 1.815–1.820 Å in pure HTS,
indicating the more relaxed structure to facilitate the
formation of five-membered cyclic Ti-OOH intermediate.23
Meanwhile, the NBO charge of Ti atom in Ni/HTS is negatively
charged with −0.027 e, which reflects that there is electron
transfer from Ni to Ti. This negatively charged the Ti site in
Ni/HTS leads to easier absorption and activation of H2O2,
resulting in the enhancement of the rate relevant step.
Oxidation-oximization of cyclohexane to cyclohexanone
oxime with CH3COONH4 as nitrogen source over the as-
synthesized Ti catalysts was initially investigated in the
presence of 30% H2O2. After extensive screening, the hollow
HTS was found to be active for this reaction, and the selectivity
to oxime was 41.8%, with the byproduct being KA-oil and
nitroso ester (Table 1, entry 2). Similarly, solid-structured TS-1
is composed of Ti species existing in tetrahedral coordination.
However, the low activity observed in the reaction using TS-1
in place of HTS (entry 3), indicates that the hollow structure of
HTS facilitates reactant transport since the reactant molecules
such as cyclohexane (0.48 nm), H2O2 (0.26 nm) and
CH3COONH4 (0.54 nm) can easily come into the intracrystalline
voids to active sites via the crystal’s channels (0.55 nm). In
contrast, another Ti-containing catalyst (entry 6), which lacks a
tetrahedral environment of the Ti atoms with very low oxime
selectivity (1.7%). As a result, the tetrahedral Ti–O4 species in
HTS are responsible for the same activation of cyclohexane
and CH3COONH4, the associated catalytic activity for the
formation of oxime. With the aim to tune the catalytic
selectivity of Ti-O4 active sites, we further studied a new
electronic structure modification of Ti-O4 sites by implanting
transition metal ions. As shown in Table 1 (entry 5),
incorporation of the Ni2+ species in the HTS is able to
significantly enhance the oxime selectivity (from 41.8% to
50.7%). On the contrary, adding Al3+, Mo3+, Cr3+ and Mn2+
species to HTS can suppress the formation of oxime (entries 8-
10). The increased selectivity over Ni-modified HTS may be due
3% Ni/HTS
HTS
Fig. 1 TEM images of HTS and 3% Ni/HTS.
The structural properties of HTS and Ni/HTS catalysts are
analyzed to elucidate the intrinsic reasons for the distinct
catalytic activity (Table S1). XRD patterns of HTS and 3%
Ni/HTS indicated that the prepared catalysts are crystalline
MFI zeolite (Fig S1),15 and the weak peak at 2Ɵ = 43.24 °
ascribed to nickel oxide clusters (JCPDS Card No. 87-0712) can
be observed. TEM imaging of HTS and Ni/HTS revealed catalyst
particles with abundant intracrystalline voids, never
connecting directly with the surface (Fig. 1). The nickel oxide
species are uniformly dispersed in hollow cavities throughout
the HTS support in the case of Ni/HTS. The presence of
intracrystalline voids accessible only via entrances smaller than
4 nm is evident from abrupt closure at p/p0 = 0.42 on the
desorption branch (Fig. 2A).16 This kind of hollow cavity
benefits diffusion and facilitates reactant transport to active
sites and increasing the catalytic activity.
The Ti coordination state of HTS and Ni/HTS catalysts was
studied by UV-visible, Fourier infrared and X-ray photoelectron
spectroscopy. Compared with the silicalite-1 or Ni/silicalite-1,
UV-visible spectra of HTS and Ni/HTS show a main band at 210
nm ascribed to tetrahedral TiO4 species,17 while a small band
at 330 nm also appears, reflecting most likely the presence of
ex-framework Ti species (Fig. 2B).18 An additional band at 280
nm (O2− to Ni2+ electron transition) is observed in Ni/HTS.19 In
Fig. S2, the characteristic band at 960 cm-1, not observed for
silicalite-1, is attributed to the stretching vibration of Si–O–Ti
bonds in the framework.20 However, this peak position shifted
to lower wavenumbers for Ni/HTS, which can be assigned to
the presence of Ni species side-on bound to the silicon of Si–
O–Ti unit, thus weakening the [Ti–O–Si] bond. Based on the Ti
2p XPS spectra (Fig. S3), the Ti 2p3/2 peak for the pure HTS is
found at the binding energy (BE) of ~ 459.1 eV belonging to the
tetrahedral TiO4 species (with a fractional amount of 72% in
Fig. S3).21 This peak for the Ni/HTS, however, displays a lower
BE, indicating that the Ti–O bonding strength was changed by
2 | J. Name., 2012, 00, 1-3
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to the formation of this Ti-O4 species with favorable electronic structure with electric charge and acid strength. In addition,
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effects, which was confirmed by calculating the Ni-modified this may be due to the formation of tDhOeI:s1t0e.1r0ic3a9l/lCy9ChCin0d9e84re0dB
HTS and the pure HTS structure (Fig.S4).
oxime–CH3COOH complex, which was incapable of entering
the HTS intracrystalline voids via the crystal’s channels (0.55
nm) as an entrance, allowing oxime to remain relatively
protected towards further oxidation. This is identified in
solution by UV-Vis spectra and calculating the diameters of the
free oxime molecule (0.51 nm) and complex (0.63 nm), as
shown in Fig. S5B and Fig. S7.
Table 1 Direct oxidation-oximization of cyclohexane to oxime over the different
catalysts.a
Sel. (%)
B
Conv.
(%)b
3.1
14.9
7.4
5.2
13.6
1.1
4.4
9.5
13.7
9.2
2.0
Entry
Catalyst
A
C
D
0
1
2
3
4
5
6
7
8
9
None
HTS
TS-1
72.5
43.1
47.3
64.0
31.2
62.7
55.8
24.5
42.6
41.6
39.3
17.6
4.3
6.5
22.1
3.2
29.4
35.1
7.3
10.0
10.9
11.7
11.4
14.9
6.3
41.8
34.5
2.6
50.7
1.7
Table 2 Direct oxidation-oximization of cyclohexane to oxime with different nitrogen
sources.a
Silicalite-1
3%Ni/HTS
2%Ti/silicalite-1
3%Ni/silicalite-1
3%Mo/HTS
3%Al/HTS
3%Cr/HTS
3%Mn/HTS
Sel. (%)
Nitrogen
source
(NH4)2SO4
NH4Cl
NH3·H2O
NH4HCO3
HCOONH4
CH3COONH4
NH3
Temp.
(°C)
110
110
90
Conv.
(%)b
36.4
18.0
4.1
0.1
1.4
13.6
9.9
Entry
A
B
C
D
2.8
2.7
57.2
16.6
19.7
50.7
29.1
9.1
0
1
2
3b
4
5
7
63.4
65.7
21.3
48.4
60.5
31.2
43.5
28.7
29.4
17.0
14.1
10.6
3.2
5.1
2.1
4.5
20.9
9.1
14.9
4.0
33.2
11.7
17.1
3.6
35.1
41.4
35.9
38.4
4.3
5.5
18.7
10
11
90
125
110
90
a
Conditions: 0.08g catalyst, cyclohexane 0.15 g (1.78 mmol), CH3COOH/CH3CN
(7.5 ml, V=1:4), ammonium acetate as an ammonium source, cyclohexane:
ammonium acetate =1:18 (molar ratio), cyclohexane:H2O2 = 1:6 (molar ratio),
reaction time 4 h at 110 °C. A = cyclohexanol; B = cyclohexanone; C = cyclohexyl
nitrite; D = cyclohexanone oxime.
8
23.4
a
Conditions: 0.08g 3%Ni/HTS catalyst, cyclohexane 0.15
g (1.78 mmol),
CH3COOH/CH3CN (7.5 ml, V=1:4), ammonium acetate as an ammonium source,
cyclohexane: ammonium acetate =1:18 (molar ratio), cyclohexane:H2O2 = 1:6
(molar ratio), reaction time 4 h at 110 °C. A = cyclohexanol; B = cyclohexanone; C
= cyclohexyl nitrite; D = cyclohexanone oxime. b Using TFA instead of CH3COOH.
Encouraged by this result, different nitrogen sources, such
as NH4Cl, (NH4)2SO4, NH4HCO3, HCOONH4, ammonia and
ammonia gas, were examined under the present reaction
conditions (Table 2). Remarkably, ammonia was also a suitable
substrate with providing the highest selectivity (57.2%), albeit
resulting in low conversion. Generally, ammonia gas and
ammonium salt from weak acids also reacted to give the
desired oxime product at 22~30% selectivity. Other
ammonium salts from strong acids such as NH4Cl and
(NH4)2SO4 gave only trace amounts of oxime products. This is
likely because ammonia can be conveniently generated in situ
through the dissociation of ammonium salt from weak acids
due to the larger N–H bond distance of the NH4+ connecting a
weak acid anion established by DFT calculations (Table S2).
Meanwhile, the N atom of ammonium salt from weak acids
with high NBO charge is more easily activated to form NH2OH
by electropositive Ti sites. The oxidation-oximization of
cyclohexane to oxime with H2O2 was also investigated using
different solvents by 3% Ni/HTS catalyst. With these solvents
such as acetonitrile, CF3COOH, CH3COOH and C2H5COOH, the
selectivity of oxime was higher than 20% under the reaction
conditions. A dramatic decrease of selectivity was observed
with ethanol. Even worse results were obtained with ethyl
acetate and t-butanol solvent, which are usually used as
solvents in cyclohexanone ammoximation reaction. Conversely,
as shown in Table S3, a dramatic improvement of selectivity
was obtained by using a mixed solvent of CH3CN and CH3COOH,
which allowed a conversion of cyclohexane close to 13.6% with
a selectivity of oxime higher than 50%. Analysis of the UV-Vis
spectra (Fig. S5A) and the continuum solvation model of DFT
calculations (Fig. S6) reveals that the beneficial co-solvent
effect can be rationalized by considering the interaction of
solvents with each other, which can modify the CH3COOH
To understand the reaction mechanism, control experiments
were performed (Table S4). When cyclohexane was explored
under standard reaction conditions in the absence of
CH3COONH4, cyclohexanone and cyclohexanol were obtained
as major products. The treatment of cyclohexanol in the same
pot resulted in the formation of the amounts of cyclohexanone
on this Ni/HTS catalyst. As stated above, it can be deduced
that the formation of cyclohexanone and cyclohexanol should
occur over Ti–O4 species from cyclohexane, and the further
conversion of cyclohexanol to cyclohexanone should also occur
over Ti–O4 species, which is also consistent with the
observation of the cyclohexanone and cyclohexanol by-
products. On the other hand, NH2OH as
a possible
intermediate was detected via Ti-catalyzed activation of
ammonia from CH3COONH4 in the absence of cyclohexane by
spectrophotography.
The reaction mechanism was also confirmed with in situ FT-
IR observation. By adding H2O2 to the reaction system (Fig S8),
the characteristic peaks of NH2OH appeared at 1023, 1227 and
1510 cm−1 assigned for the ν(N-O), ν(N-O-H) and ν(NH2),
respectively.24 Besides these, the appearance of the
characteristic band at 1701 cm−1, attributed to ν(C=O),25 was
taken as evidence of cyclohexanone formation. As the reaction
proceeded, these peak strengths began to increase gradually
and then reduced rapidly, indicating that cyclohexanone and
NH2OH were formed and further transformed as intermediates.
At the same time, the new characteristic modes of ν(C=N) and
ν(N–O) of cyclohexanone oxime at 1667 and 985 cm−1
coalesced,24c,26 which confirms the occurrence of the
oximization to oxime. In addition, the very small ν(C=N)
vibration around 1655 cm−1 indicates the imine formation.25 In-
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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8
9
M. G. Clerici and P. Ingallina, Journal of Catalysis, 1993, 140,
situ FT-IR spectra further allowed monitoring the NH2OH
formation in absence of cyclohexane (Fig. S8). A band
developing initially at 1101 cm−1 can be assigned to NH3 from
the dissociation of CH3COONH4 before reaction in CH3CN-
CH3COOH co-solvent. After the addition of H2O2, the
characteristic band of NH2OH shows that NH2OH is generated.
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71-83.
DOI: 10.1039/C9CC09840B
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Chemistry, 2015, 17, 3378-3389.
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On the basis of the above results and previous reports,23a,27
a
plausible mechanism is proposed in Fig S9. In this mechanism,
framework Ti in HTS interacted with H2O2 giving rise to the
formation of Ti–OOH species,28 which was responsible for the
C–H bond activation of cyclohexane to produce cyclohexanone
and cyclohexanol. Meanwhile, an initial attack of Ti–OOH
species onto the N–H of ammonia from CH3COONH4 affords
the intermediate NH2OH, followed by oximization of
cyclohexanone to generate oxime as a major pathway.27b
Alternatively, the formed cyclohexanone directly condenses
with ammonia to form imine, which is then oxidized to product
oxime.
In summary, direct oxidation-oximization of cyclohexane to
cyclohexanone oxime with 30% H2O2 was achieved by using a
peculiar CH3CN-CH3COOH cosolvent and an improved HTS
catalyst by means of the introduction of Ni ((Ni/HTS).
Mechanistic studies indicated that NH2OH and cyclohexanone
as possible intermediates involved in our catalytic system. The
simplicity of this one-step process, and the demonstrated
possibility of the raw material transformation, make this
methodology particularly attractive for a possible industrial
development.
This work was supported by the Natural Science Foundation
of China (Grant No. 21576078, 21878074 and 21978078).
20 (a) X. Wang, X. Zhang, Y. Wang, H. Liu, J. Qiu, J. Wang, W.
Han and K. L. Yeung, Chemistry of Materials, 2011, 23, 4469-
4479; (b) M. Wang, J. Zhou, G. Mao and X. Zheng, Industrial
& Engineering Chemistry Research, 2012, 51, 12730-12738.
21 (a) C. Pang, J. Xiong, G. Li and C. Hu, Journal of catalysis,
2018, 366, 37-49; (b) M. Capel-Sanchez, J. Campos-Martin, J.
Fierro, M. De Frutos and A. P. Polo, Chemical
Conflicts of interest
There are no conflicts to declare.
Communications, 2000, 855-856.
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DOI: 10.1039/C9CC09840B
Figure-abstract
Highlights
► One-step preparation of cyclohexanone oxime from cyclohexane and ammonium
acetate.
►13.6% cyclohexane conversion and 51% cyclohexanone oxime selectivity are achieved.
► Tetrahedral TiO4 sites allows to activate simultaneously the different reactants.
► Varieties of different ammonias as readily available starting materials.