Ferric(III) nitrate supported on kieselguhr: A new reagent for selective oxidation of alcohols

Article abstract of DOI:10.1080/00397910600775309

A selective and effective oxidation of alcohols into the corresponding aldehydes and ketones, respectively, with a new reagent, ferric(III) nitrate supported on kieselguhr, under heterogeneous conditions is reported. Copyright Taylor & Francis Group, LLC.

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Ferric(III) Nitrate Supported on Kieselguhr:
A New Reagent for Selective Oxidation of
Alcohols
Ji‐Dong Lou a , Long‐Hua Zhu a , Yi‐Chun Ma a & Li Li b
a College of Life Sciences , China Institute of Metrology , Hangzhou,
Zhejiang, China
b Instituto Superior Tecnico , Lisbon, Portugal
Published online: 16 Feb 2007.
To cite this article: Ji‐Dong Lou , Long‐Hua Zhu , Yi‐Chun Ma & Li Li (2006) Ferric(III) Nitrate Supported
on Kieselguhr: A New Reagent for Selective Oxidation of Alcohols, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 36:20, 3061-3064, DOI:
10.1080/00397910600775309
To link to this article: http://dx.doi.org/10.1080/00397910600775309
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Synthetic Communicationsw, 36: 3061–3064, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600775309
Ferric(III) Nitrate Supported on
Kieselguhr: A New Reagent for Selective
Oxidation of Alcohols
Ji-Dong Lou, Long-Hua Zhu, and Yi-Chun Ma
College of Life Sciences, China Institute of Metrology,
Hangzhou, Zhejiang, China
Li Li
Instituto Superior Tecnico, Lisbon, Portugal
Abstract: A selective and effective oxidation of alcohols into the corresponding
aldehydes and ketones, respectively, with a new reagent, ferric(III) nitrate supported
on kieselguhr, under heterogeneous conditions is reported.
Keywords: Alcohol, ferric(III) nitrate, kieselguhr, oxidation
INTRODUCTION
It is well known[1,2] that the benefits of using supported reagents for organic
synthesis are considerable, especially because they offer remarkable ease of
handling and use; often one can simply weight the amount of reagent to be
used. At the end of the reaction, a filtration suffices to remove the contami-
nating by-products. Solvent evaporation from the filtrate is often sufficient
to provide the product in pure form. Likewise, reagent recovery or generation
can also be very easy. Solid-supported reagents are relatively safe to handle
because of the full chemsorption of the possible toxic chemicals.
Received in R.O.C. March 11, 2006
Address correspondence to Ji-Dong Lou, College of Life Sciences, China Institute
of Metrology, Hangzhou, Zhejiang 310018, China. E-mail: lou@cjlu.edu.cn
3061

3062
J.-D. Lou et al.
RESULTS AND DISCUSSION
The oxidation of primary and secondary alcohols to the corresponding
aldehydes and ketones has been accomplished with a large number of
.
oxidative reagents. So far ferric(III) nitrate nonahydrate [Fe(NO3)3 9H2O]
supported on various inorganic supports has been employed as an oxidizing
reagent for transformations; for example, ferric(III) nitrate supported on
silica gel,[3] ferric(III) nitrate supported on K 10-clay,[4] and ferric(III)
nitrate supported on HZSM-5 zeolite.[5] These supported reagents have
achieved good selectivity under mild reaction conditions and convenient
isolation of the products. Another advantage is the reduction in product con-
tamination assured by having the reagent fully bound to a solid support. This is
very important for oxidation reactions so that overoxidation reactions can be
minimized. However, they have some typical problems with their stabilities,
so searching for new experimental procedures for conducting oxidations
with ferric(III) nitrate–based reagents is still of interest.
Previously, we have found that kieselguhr is a good inorganic solid
support for both chromic acid[6] and potassium permanganate[7] for the
selective oxidation of alcohols to carbonyl compounds. Based on our
previous study,[6,7] we now report that ferric(III) nitrate supported on kiesel-
guhr is a new reagent suitable for the selective oxidation of primary and
secondary alcohols into the corresponding aldehydes and ketones, respect-
ively (Scheme 1).
The present reagent is easily prepared by grinding ferric(III) nitrate non-
ahydrate and kieselguhr. The oxidation is very simple. After contact of the
alcohols with ferric(III) nitrate supported on the kieselguhr reagent, the
expected products are obtained. Our results are reported in Table 1.
Compared with some other existing ferric(III) nitrate–supported
reagents, the advantage of the present method is mainly that the solid
reagent is more stable. For instance, ferric(III) nitrate–silica gel should be
used directly for the oxidation after preparation and it is unknown how long
this reagent can be kept;[3] ferric(III) nitrate–K 10 clay can be kept without
special care for around only 2 weeks;[4] and the stability of ferric(III)
nitrate–HZSM-5 zeolite looks better than that of ferric(III) nitrate–K 10-
clay reagent.[5] However, in our case, the present reagent can be stored in a
dark brown vacuum dryer without loss of activity for at least 6 months.
Also, with this reagent, the reaction times are shorter and the support is
much cheaper. Furthermore, some quite sensitive functionalized alcohols,
for instance, acetate and diol, are first tested with ferric(III) nitrate–supported
Scheme 1.

Table 1. Oxidation of alcohols with ferric(III) nitrate supported on kieselguhr reagent
Bp/8C/mm
Mp/8C of 2,4-DNP
Found
Reported[8]
Reaction
time (h)
Yieldc
(%)
Substratea
Productb
PhCHO
PhCH55CHCHO
p-H3CO-C6H4-CHO
CH255CHC(O)CH3
CH3CH2C(O)CH3
Found
Reported[8]
PhCH2OH
1
97
95
93
91d
95
95
55–58/10
120–122/10
120–123/10
178–179
248
248
237–239
255–257
252–254
139–140
113–115
161–163
237
255
PhCH55CHCH2OH
p-H3CO-C6H4-CH2OH
CH255CHCH(OH)CH3
CH3CH2CH(OH)CH3
1
1
254
1
139.5–140.5
115
161–162
1.5
1.5
78–80/760
153–155/760
80
155
PhCH(OH)Ph
PhCH(OH)COOC2H5
PhCH(OH)CH2OH
1
1
1
1
PhC(O)Ph
PhCOCOOC2H5
PhCOCH2OH
98
91
93
90
116–119/0.9
126–129/10
110–113/10
59–62/10
305
130/10
118–120/11
162.5–163
47–49e
48–49e
231–234
193–194
233–236
193–194
aAll the substrates are commercially available.
bAll the aldehydes and ketones have been described previously in the literature and were identified by their IR spectra or by the IR spectra
and melting points of their 2,4-dinitrophenylhydrazones.
cYield of isolated product.
dIsolated as the 2,4-dinitrophenylhydrazone.
eMp of benzophenone.

3064
J.-D. Lou et al.
reagents without causing any problems. The present procedure, therefore,
offers clear benefits over the earlier reported methods.
EXPERIMENTAL
Preparation of Ferric(III) Nitrate Supported on Kieselguhr Reagent
.
The reagent is prepared by grinding Fe(NO3)3 9H2O (4 g, 10 mmol) and
kieselguhr (12 g) in an agate mortar to form a mixture of about 15 g, which
can be directly used for oxidation. This new Fe(NO3)3–kieselguhr reagent
can be stored in a dark brown vacuum dryer without loss of activity.
Oxidation of Benzyl Alcohol to Benzaldehyde: Typical Procedure
The Fe(NO3)3–kieselguhr reagent (1.8 g) is placed in a flask together with
CH2Cl2 (15 mL), and the mixture is magnetically stirred. A solution of
benzyl alcohol (108 mg, 1 mmol) in CH2Cl2 (3 mL) is added, and after 1 h
at gentle reflux, the solid is filtered and washed with CH2Cl2 (3 Â 5 mL).
The combined filtrates are evaporated to give the crude product, which is
purified by preparative thin-layer chromatography (TLC) with hexane–ethyl
acetate (8:2) to afford 103 mg (97%) benzaldehyde (Table 1).
REFERENCES
1. Laszlo, P. Preparative Chemistry using Supported Reagents; Academic Press: San
Diego, CA, 1987.
2. Mckillop, A.; Young, D. W. Organic synthesis using supported reagents. Synthesis
1979, 401, 481.
3. Khadikar, B.; Borkar, S. Silica gel supported ferric nitrate: A convenient oxidizing
reagent. Synth. Commun. 1998, 28, 207–212.
4. Cornelis, A.; Laszlo, P. Oxidation of alcohols by clay-supported iron(III) nitrate: A
new efficient oxidizing agent. Synthesis 1980, 849–850.
5. Heravi, M. M.; Ajami, D.; Mojtahedi, M. M.; Ghassemzadeh, M. “Zeofen,” a user-
friendly oxidizing reagent. Chem. Commun. 1999, 833–834.
6. Lou, J.-D. Chromic acid adsorbed on kieselguhr: A new reagent for the oxidation of
primary alcohols to aldehydes. Synth. Commun. 1989, 19, 1841–1845.
7. Lou, J.-D.; Lou, W.-X. Oxidation of alcohols to carbonyl compounds with a new
potassium permanganate adsorbed on kieselguhr reagent. Synth. Commun. 1997,
27, 3697–3699.
8. Buckingham, J. Dictionary of Organic Compounds, 6th ed.; Chapman and Hall:
Cambridge, 1996.