Facile preparation and reactivity of magnetic nanoparticle-supported hypervalent iodine reagent: A convenient recyclable reagent for oxidation

Article abstract of DOI:10.1002/adsc.201100601

A simple three-step preparation of magnetic nanoparticle-supported (diacetoxyiodo)benzene starting from 4-iodobenzoic acid is described. The nanoparticle reagent was obtained with good loading levels and has been successfully used for efficient oxidation

Full text of DOI:10.1002/adsc.201100601

COMMUNICATIONS
DOI: 10.1002/adsc.201100601
Facile Preparation and Reactivity of Magnetic Nanoparticle-
Supported Hypervalent Iodine Reagent: A Convenient
Recyclable Reagent for Oxidation
Chenjie Zhua and Yunyang Weia,*
a
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, Peopleꢀs Republic of
China
Fax : (+86)-25-8431-7078; phone: (+86)-25-8431-5514; e-mail: ywei@mail.njust.edu.cn
Received: July 29, 2011; Published online: January 19, 2012
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.201100601.
Abstract: A simple three-step preparation of mag-
netic nanoparticle-supported (diacetoxyiodo)ben-
zene starting from 4-iodobenzoic acid is described.
The nanoparticle reagent was obtained with good
loading levels and has been successfully used for ef-
ficient oxidation of a wide range of alcohols. The
supported reagent demonstrated comparable activi-
ty with that of its homogeneous counterpart (diacet-
can be efficiently separated from reaction mixtures
and reused.[3] Taking PhI
(OAc)2 as an example to ad-
AHCTUNGTRENNUNG
dress the recovery issue, many highly efficient strat-
egies have been used to immobilize this reagent onto
various supports such as organic and inorganic poly-
mers (a–d),[4] perfluorous alkyl chains (e),[5] and ionic
liquids (f, g)[6] (Figure 1). However, substantial de-
creases in activity (or efficiency) of these immobilized
reagents are frequently observed due to the heteroge-
neous nature of these support materials in reaction
media. Furthermore, in many instances recovery of
heterogenized reagents through filtration is cumber-
some, especially in the case of air-sensitive or high
toxicity products. To overcome the low reactivities of
heterogeneous recyclable hypervalent reagents, solu-
ble recyclable alternatives having comparable reactiv-
ACHTUNGTRENNUNGoxyiodo)benzene and could be simply recycled with
the assistance of an external magnet.
Keywords: alcohols; aldehydes; hypervalent iodine
compounds; oxidation; supported catalysts
ities to PhI
In recent years, hypervalent iodine compounds have groups of Kita,[7a,b] Togo,[7c] and Zhdankin.[7d]
been used extensively for a variety of chemical trans- On the other hand, magnetite or maghemite
ACHTUNGRTEN(NUNG OAc)2 have also been developed by the
formations and particularly as reagents in several oxi- (Fe3O4/g-Fe2O3) nanoparticles (MNP) have drawn
dation reactions.[1] As a result of their non-toxic considerable attention as heterogeneous catalytic sup-
nature, affordability, and safety profile, hypervalent ports for their good stability, high surface area and
iodine compounds are nowadays popular reagents for easy synthesis.[8] The direct use of MNP without modi-
the formation of carbon-carbon bonds, carbon-heter- fication as magnetically recoverable catalysts for or-
oatom bonds, and heteroatom-heteroatom bonds. Ac- ganic reactions has also been explored.[9] An attrac-
tivation of carbon-hydrogen bonds, rearrangements, tive feature of MNP-supported catalysts is that they
and fragmentations can be also induced by these re- can be easily separated with the aid of an external
agents. Despite the synthetic importance of hyperva- magnet, thus facilitating easy catalyst recycling with-
lent iodine compounds, their broader application has out using extra organic solvents and additional filtra-
been restricted due to the low atom economy, because tion steps.[10] In addition, crystalline nanoparticles
the use of stoichiometric amounts of hypervalent with appropriate surface coatings are readily dispersi-
iodine reagents leads to the production of equimolar ble in organic solvents and catalysts are usually immo-
amounts of organic iodine waste, such as PhI, which is bilized on the surface of nanoclusters. Reactants in
difficult to recover and reuse because of the high vol- solution have easy access to the active sites on the
atility and solubility in organic solvents. A possible surface of nanoparticles, avoiding the problems en-
solution would be the development of catalytic sys- countered in many heterogeneous support matrixes
tems based on hypervalent iodine.[2] Another is the where a great portion of the catalysts are present
application of recyclable reagents, whose by-products deep inside the matrix backbones and reactants have
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Chenjie Zhu and Yunyang Wei
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Figure 1. Examples of supported PhIACTHNUTRGENUG(N OAc)2 reagents.
only limited access to the catalytic sites. Furthermore, have a large affinity for under-coordinated surface
the magnetically functionalized reagents often show sites of metal oxide particles.[13] Reaction of 3-amino-
identical and sometimes even higher activity than propyltriethoxysilane with 4-iodobenzoic acid using
their corresponding homogeneous analogues due to diisopropylcarbodiimide (DIC) in combination with
the high accessible surface area.[11]
1-hydroxybenzotriazole (HOBt) afforded 1 in excel-
To the best of our knowledge, no example of a lent yields. Polyvinylpyrrolidone (PVP, average MW:
magnetic nanoparticle-supported hypervalent iodine 40,000)-protected magnetic nanoparticles of 8–20 nm
reagent has been reported. Therefore, we envisaged were prepared by coprecipitation of ironACTHNUTRGNE(NUG III) and
that use of MNP as a support would properly address iron(II) ions in basic solution following the published
the efficiency issues in hypervalent iodine reagents by procedure.[14] The obtained MNP were sonicated for
providing a readily recyclable and reusable oxidant one hour before being treated with excess 1 in anhy-
with reasonably high activity. In continuation of our drous toluene under reflux. Subsequent oxidation to
efforts to develop new applications of hypervalent derivative 3 was accomplished using freshly prepared
iodine reagents,[12] here, we would like to report our peracetic acid at 408C overnight. The loading of 3 is
exploration of the design of MNP-supported 0.68 mmol/g as determined by elemental analysis.
PhI
hols.
MNP-supported PhI
synthesized according to the procedure shown in
G
ACHTUNGTRENNUNG(OAc)2
AHCTUNGTRENNUNG
Scheme 1. Organic silane groups were chosen for im- acterized by FT-IR spectroscopy, transmission elec-
mobilization of PhI complexes to the surface of mag- tron microscopy (TEM), scanning electron microsco-
netite nanoparticles because silanes were known to py (SEM), powder X-ray diffraction (XRD), vibrating
Scheme 1. Synthesis of the MNP-supported PhIACHTNUTRGENNUG(OAc)2 (3) and SiO2-supported PhIACHTUNTGERN(NUNG OAc)2 (5).
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Facile Preparation and Reactivity of Magnetic Nanoparticle-Supported Hypervalent Iodine Reagent
Figure 2. TEM images of MNP-PIDA (3): (left) before reac-
tion and (right) after reusing 8 times.
sample magnetometer (VSM), thermogravimetric
analysis (TG-DTG) and elemental analysis.[15] Un-
fortunately, due to the magnetic properties of 3 it is
actually impossible to further characterize this materi-
al by using solid state NMR spectroscopy.[16] From the
Figure 3. Magnetization curve of MNP-PIDA measured at
room temperature.
transmission electron microscopy (TEM) analyses of tion to afford the corresponding aldehydes or ketones
MNP-PIDA 3, it was confirmed that well separated in excellent yield. The present protocol afforded alde-
nanoparticles with a size distribution ranging from 8 hydes from primary alcohols and ketones from secon-
to 20 nm were homogeneously dispersed over the dary alcohols. Excellent chemoselectivity was ob-
entire area (Figure 2, left), such polydispersity is ex- served under the present system. We detected no
pected from of the protocol chosen for the synthesis phenol oxidation products (Table 1, entry 6), which
of magnetic nanoparticles. Note that the particles are well known to form in reactions with aryl-l3-io-
showed slight aggregation after 8 times recycling danes.[18] In the oxidation of primary alcohols to the
(Figure 2, right), presumably because the moieties on corresponding aldehydes, no signs of any over-oxida-
the MNP surfaces are less effective in preventing the tion to their carboxylic acids, even after prolonged re-
aggregation of the MNP (upon solvent evaporation). action times, were detected. An allylic alcohol such as
However, powder X-ray diffraction (XRD) indicated cinnamyl alcohol (Table 1, entry 9) was also oxidized
that the final MNP-PIDA was oxidized from magnet- efficiently without any observable reaction at the
ite (Fe3O4) to maghemite (g-Fe2O3),[15] on the basis of double bond functionality. In the present research
the calculations with the Debye–Scherrer formula, the benzylic alcohols underwent smooth oxidation
mean grain size of maghemite was 18.3 nm, which is (Table 1, entries 1–7). The electronic properties of the
consistent with the TEM images. The magnetic prop- substituents in the aromatic ring had A relatively
erties of MNP-PIDA were determined by vibrating minor influence on the oxidation of alcohols (Table 1,
sample magnetometer (VSM), the magnetization entries 2 and 4). Strong electron-withdrawing groups,
curve of MNP-PIDA exhibited typical superparamag- such as nitro group, improve the oxidation of alcohol
netic behavior, showing no observed hysteresis (Table 1, entry 2). Strong electron-donating groups,
(Figure 3). The saturation magnetization value (ss) is such as the OCH3 group, lowered the reaction rate
51.32 emu/g. The value is slightly smaller than that of (Table 1, entry 4). This is different from previously re-
bulk magnetite (92 emu/g), which is probably due to ported procedures where the OCH3 group favors al-
the increasing amount of non-magnetic material (or- cohol oxidation.[19] Heteroaryl alcohols such as 2-
ganic ligands) on a particle surface which makes a furyl, 2-thienyl, and 3-pyridinyl alcohols also gave
larger percentage of the particle mass non-magnetic. good yields (Table 1, entries 11–13). It is worth men-
However, this value is sufficiently high for magnetic tioning that together with the good results with ben-
separation. The final MNP-PIDA is well dispersed in zylic, allylic and heteroaryl alcohols, the yields ob-
common organic solvents and can be efficiently at- tained from the reaction of aliphatic alcohols under
tracted with a small magnet.
the same conditions are also quite high (Table 1, en-
In order to check the efficiency of MNP-PIDA, the tries 15 and 16). In view of the fact that the reaction
known PIDA/TEMPO oxidation system was select- of an aliphatic alcohol is much more difficult than the
ed.[17] The MNP-PIDA was then tested for the oxida- reaction of a benzylic alcohol, the results obtained
tion of a wide range of alcohols, including benzylic, with the present procedure were very satisfactory.
allylic, heterocyclic, alicyclic, and aliphatic alcohols.
As can be seen in Table 1, the use of SiO2-PIDA
As shown in Table 1, most alcohols underwent oxida- (5) instead of MNP-PIDA (3) in the oxidation of alco-
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Chenjie Zhu and Yunyang Wei
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Table 1. Oxidation of alcohols.
Entry
1
Alcohols
Products
System[a]
Time [h]
Yield [%][b]
A
B
1.0
2.0
94
92
A
B
0.5
1.5
96
90
2
3
4
5
6
A
B
1.0
2.0
94
90
A
B
2.5
4.0
90
87
A
B
1.0
2.0
92
88
A
B
1.0
1.5
93
91
A
B
2.0
3.0
95
92
7
8
A
B
4.0
5.0
90
86
A
B
1.5
2.0
96
93
9
A
B
4.0
6.0
88
80
10
A
B
A
B
A
B
3.0
5.0
2.0
4.0
2.0
4.0
91
87
88
81
93
90
11
12
13
A
B
A
B
5.0
7.0
4.0
6.0
78
70
88
82
14[c]
15[c]
A
B
5.0
7.0
85
79
16[c]
[a]
Oxidation system A: MNP-PIDA/TEMPO, B: SiO2-PIDA/TEMPO.
Yields of isolated products unless otherwise noted.
Yields were determined by GC-MS.
[b]
[c]
hols led to similar results, albeit a longer reaction This is because when the size of the support materials
time was needed. For a comparison of the activities of is decreased to the nanometer scale, the surface area
3, 5, and PhIACHTUNGTRENNUNG(OAc)2, the experiments on the reaction of nanoparticles will increase dramatically. For exam-
rate were carried out using benzyl alcohol as the ple, spherical nanoparticles of 10 nm diameter have a
model substrate. The MNP-PIDA showed excellent calculated surface area of 600 m2 cmÀ3, which is com-
activity toward the oxidation of alcohol, which is com- parable to that of many porous supports for reagent
parable to that of its homogeneous counterpart immobilization. As a consequence, nanoparticle sup-
PhIACHTUNGTRENNUNG(OAc)2, as presented in Figure 4. Although the ac- ports could have a higher loading capacity than many
tivity of 3 is a little lower than that of its homogene- other conventional support matrixes, leading to the
ous counterpart, probably due to steric and diffusion improved activity of the nanoparticle-supported re-
rate differences, the relative activity of 3 seems to be agents. Another and far more important reason for
extraordinarily higher than that of SiO2-PIDA (5), this phenomenon is that the nanometer-sized supports
suggesting the importance of a nanosized support. will even be dispersible in solution, forming an emul-
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Facile Preparation and Reactivity of Magnetic Nanoparticle-Supported Hypervalent Iodine Reagent
Table 2. Competitive oxidation of primary and secondary al-
cohols.[a]
Entry
Substrate
Product
Time [h]
1
Yield [%][b]
92
+
1
<5
85
+
–
2
4
[a]
The reactions were carried out on a 1:1 mixture of pri-
mary and secondary alcohols, on a 1 mmol scale.
GC-MS yield.
Figure 4. Comparison of the oxidation activities of PIDA,
MNP-PIDA and SiO2-PIDA.
[b]
Figure 5). After the reaction, the organic layer was
simply decanted, assisted by a nearby magnet, to
afford the desired products. The MNP-PIDA was
quickly concentrated to the side wall of the reaction
vial once a magnet is placed nearby. The separated
MNP-PIDA was then washed and regenerated by
treatment with peracetic acid. The reusability of the
reagent was investigated by the oxidation of benzyl
alcohol. The procedure was repeated and the results
indicated that the reagent could be recycled for 8
times with no apparent loss of acitivity (Figure 6).
TEM shows that the MNP-PIDA still maintained the
nanostructure after repeated reuse, proving its robust-
ness (Figure 2). More importantly from the point of
view of an application, it is possible to remove the re-
agent completely after the reaction. This aspect was
checked by the following experiment. During the re-
action, the MNP-PIDA was attracted to the bottom of
the reactor by the application of a magnetic field.
Then, about half of the supernatant was transferred
Figure 5. (1) Reaction mixture containing MNP-PIDA; (2)
MNP-PIDA collected using an external magnet after the re-
action.
sion (see Figure 5), therefore, the present nanomag- to a new reactor. The solution was averagely divided
net-supported reagent 3 can be regarded as a “quasi- into two sections S1 (without MNP-PIDA) and S2
homogeneous” reagent.
(containing MNP-PIDA). The conversion of the alco-
Table 2 shows the results of the competitive oxida-
tion of primary and secondary alcohols. The compet-
ing oxidation of an equimolar mixture of benzyl alco-
hol and 1-phenylethanol resulted in a 92% yield of
benzaldehyde and less than 5% yield of acetophenone
(Table 2, entry 1). Oxidation of an equimolar mixture
of octan-1-ol and octan-2-ol gave 85% caprylic alde-
hyde, whereas no ketone could be detected (Table 2,
entry 2). These results suggest that the chemoselective
oxidation of a primary alcoholic functionality in the
presence of a secondary alcoholic functionality is pos-
sible with the present oxidation system.
Product separation and recycling of the MNP-
Figure 6. Recycling esperiments for the oxidation of benzyl
PIDA were indeed quite easy and simple (see alcohol.
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5.0 mmol), and the solution was stirred at room temperature
for 12 h. After completion, the crude product was purified
by column chromatography (petroleum ether/ethyl acetate=
3/1) to give the product 1; yield: 2.08 g (92%). 1H NMR
(500 MHz, CDCl3): d=7.99 (s, 1H), 7.75 (d, J=8.5 Hz, 2H),
7.51 (d, J=8.5 Hz, 2H), 3.82 (q, J=7.0 Hz, 6H), 3.41–3.45
(m, 2H), 1.71–1.77 (m, 2H), 1.21 (t, J=7.0 Hz, 9H), 0.68–
0.71 (m, 2H).
hol in S1 and S2 was 27% via GC-MS. After an addi-
tional one hour, the conversions of the alcohol in S1
and S2 were 29% and 91%, respectively. These ex-
periments prove that the MNP-PIDA can be almost
completely separated from the reaction solution. This
could be further supported by the fact that only 0.8%
loss of weight in MNP-PIDA was observed after eight
times recycling. The possibility for recovery of the
MNP-PIDA by magnetic decantation is clearly advan-
tageous in comparison to conventional filtration pro-
tocols for SiO2-PIDA which, in our experience, always
go along with some loss of weight.
In conclusion, we have prepared MNP-PIDA as a
first maghemite nanoparticles-supported hypervalent
iodine reagent. The prepared MNP-PIDA allowed the
oxidation of alcohols to aldehydes or ketones in ex-
cellent yields and high selectivity without remarkable
over-oxidation to carboxylic acids. It is noteworthy to
mention that the reagent could easily be recycled and
reused without loss of activity. This new reagent can
be regarded as a readily available alternative or as a
complement to the known supported hypervalent
iodine reagents.
Synthesis of PVP-Stabilized Magneitite Nanoparticles
FeCl3·6H2O (11.0 g, 40.7 mmol) and FeCl2·4H2O (4.0 g,
20.4 mmol) were dissolved in 60 mL deionized water under
nitrogen gas with vigorous stirring at 858C. The pH value of
the solution was adjusted to 9 by addition of concentrated
NH3·H2O. After 4 h, the magnetite precipitates were washed
to pH 7 by deionized water. The black precipitate was col-
lected with a permanent magnet under the reaction flask,
and the supernatant was decanted. The sediment was re-dis-
persed in 50 mL of deionized water. The PVP aqueous solu-
tion (5.0 mL, 25.6 g/L) was added, and the mixture stirred
for 1 day at room temperature. The PVP-stabilized magnet-
ite nanoparticles were separated by addition of aqueous ace-
tone (H2O/acetone=1/10, v/v) and centrifugation at
10000 rpm for 5 min. The supernatant solution was removed,
and the precipitated particles were washed by ethanol twice.
The particles were dried under vacuum.
Experimental Section
Synthesis of MNP-PIDA (3)
1.0 g of PVP-stabilized magneitite nanoparticles was dis-
persed in 30 mL dry toluene by sonication for 1 hour. Com-
pound 1 (1.35 g, 3.0 mmol) was then added. The reaction
mixture was refluxed under nitrogen gas for 3 days. After
being cooled to room temperature, the products were sedi-
mented on a magnet and washed successively with dry tolu-
ene (50 mLꢂ3) and dry acetone (50 mLꢂ2), then dried
under vacuum. Acetic anhydride and hydrogen peroxide so-
lution (30%) were mixed in a 2:1 ratio and stirred for 5 h at
408C. This peracetic acid solution was added to the com-
pound 2 (about 20 mL per gram) at 408C and the mixture
stirred overnight. After reaction, the product was collected
by a magnet and washed with toluene. The loading of 3 is
0.68 mmolgÀ1 as determined by elemental analysis.
General Methods
1H NMR spectra were obtained with TMS as internal stan-
dard in CDCl3 using a Bruker DRX 500 (500 MHz) spec-
trometer. GC-MS were recorded on a Thermo Trace DSQ
GC-MS spectrometer using a TRB-5MS (30 mꢂ0.25 mmꢂ
0.25 mm) column. ESI-MS were recorded on a Thermal Fin-
nigan TSQ Quantum ultra AM spectrometer using a TRB-
5MS (30 mꢂ0.25 mmꢂ0.25 mm) column. The shape and sur-
face morphology of the samples were examined on a scan-
ning electron microscope (SEM) (Hitachi S-3400N, Japan).
Transmission electron microscope (TEM) images were ob-
tained from a JEOL JEM-2010 instrument. X-ray diffraction
(XRD) images were obtained from a Rigaku D/max-
2400PC instrument with Cu Ka radiation. Elemental analy-
sis was performed on an Elementar Vario MICRO spec-
trometer. Magnetic measurements of particles were made
using a vibrating sample magnetometer (Lake Shore 7410).
Thermogravimetric analysis was carried out in nitrogen
using a Shimadzu TGA-50 spectrometer. IR spectra were
recorded on a Nicolet IS10 spectrometer. Silica gel (60–100
mesh) was dried at 2008C for 5 h before use. All solvents
used were strictly dried according to standard operations
and stored over 4 ꢃ molecular sieves. All other chemicals
(AR grade) were obtained from commercial resources and
used without further purification.
Synthesis of SiO2-Supported PhIACTHNUTRGEN(UNG OAc)2 (5)
Silica gel (60–100 mesh) was dried at 2008C for 5 h before
use. Then 1.0 g of active silica was dispersed in 30 mL dry
toluene by sonication for 1 hour. Compound 1 (1.35 g,
3.0 mmol) was then added. The reaction was refluxed for 3
days under nitrogen gas. After being cooled to room tem-
perature, the products were collected by filtration and
washed successively with dry toluene (50 mLꢂ3) and dry
acetone (50 mLꢂ2). The obtained powder was then dried
under vacuum. After completion, a similar work-up proce-
dure was followed as mentioned above to afford 5. The
loading of 5 is 0.53 mmolgÀ1 as determined by elemental
analysis.
Synthesis of Compound 1
To
5.0 mmol) in CHCl3 (20 mL) was added 3-aminopropyltri-
ethoxysilane (1.11 g, 5.0 mmol), diisopropylcarbodiimide
a stirred solution of 4-iodobenzoic acid (1.24 g,
ACHTUNGTRENNUNG
(0.63 g,
5.0 mmol),
1-hydroxybenzotriazole
(0.68 g,
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Adv. Synth. Catal. 2012, 354, 313 – 320

Facile Preparation and Reactivity of Magnetic Nanoparticle-Supported Hypervalent Iodine Reagent
[3] For reviews on supported hypervalent iodine reagents,
Oxidation of Alcohols by MNP-PIDA
see: a) H. Togo, Eco Ind. 2002, 7, 5; b) H. Togo, K. Sa-
kuratani, Synlett 2002, 1966; c) H.-J. Frohn, M. E.
Hirschberg. A. Wenda, V. V. Bardin, J. Fluorine Chem.
2008, 129, 459; d) M. Uyanik, K. Ishihara, Chem.
Commun. 2009, 2086; e) M. S. Yusubov, V. V. Zhdan-
kin, Mendeleev Commun. 2010, 20, 185.
Reagent 3 (1 mmol) was added to a solution of alcohol
(1 mmol) and TEMPO (0.01 g, 0.05 mmol) in CH2Cl2
(10 mL). The resulting solution was stirred at room temper-
ature and monitored by gas or thin-layer chromatography.
After completion, 3 was collected at the side of the flask
using a small magnet, and the supernatant carefully deca-
nted. Particles were then washed and regenerated by treat-
ment with peracetic acid. The organics were concentrated
under vacuum to yield the corresponding carbonyl com-
pound.
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Oxidation of Alcohols by SiO2-PIDA
Reagent 5 (1 mmol) was added to a solution of alcohol
(1 mmol) and TEMPO (0.01 g, 0.05 mmol) in CH2Cl2
(10 mL). The resulting solution was stirred at room temper-
ature and monitored by gas or thin-layer chromatography.
After completion, 5 was collected by filtration for reuse.
The filtrate was evaporated to give the corresponding car-
bonyl compound.
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We are grateful for the financial support from Nanjing Uni-
versity of Science and Technology, and Project supported by
the Research and Innovation Plan for Graduate Students of
Jiangsu Higher Education Institutions (No. CX2211 0266).
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