11th European Congress on Catalysis – EuropaCat-XI, Lyon, France, September 1st-6th, 2013

Green oxidation of cyclohexanol and hydroxyacetone with H2O2

catalyzed by FeCl3 in the dark and under light irradiation
D. Mandelli*,1, J. E. Arruda1, G. B. Shul’pin 2, R. V. Busto1, W. A. Carvalho1
1
Universidade Federal do ABC, Centro de Ciências Naturais e Humanas, Av. dos Estados, 5001, Bairro Bangu,
Santo André – São Paulo – Brasil, CEP: 09210-580
2
Semenov Institute of Chemical Physics, Russian Academy of Sciences, ul. Kosygina, dom 4, Moscow 119991, Russia
(*) corresponding author: dalmo.mandelli@ufabc.edu.br

Keywords: Renewables, alcohols, glycerol, hydrogen peroxide, iron, green chemistry

1 Introduction
As abundant bio-renewable feedstock from the biodiesel manufacture, glycerol, is a very important compound
[1]. Oxidative transformations of glycerol are especially important from the industrial point of view. Many methods
of glycerol oxidation employing air or molecular oxygen have been reported using heterogeneous catalytic systems,
but the homogeneous oxidation of glycerol by peroxides remained almost unstudied. Recently, some of us disclosed
the first homogeneous catalytic systems for oxidative transformations of glycerol which are based on osmium ([2]),
manganese [3] and copper [4] complexes as catalysts and which use H2O2 or t-BuOOH as oxidants. Continuing our
search for new catalytic systems efficient in the alcohol and especially glycerol oxidation under mild conditions we
decided to apply for this reaction very cheap and ecologically friendly catalyst FeCl 3 which has been previously
demonstrated by some of us to be efficient in the thermal oxidation of alkanes [5] and alcohols [2a,b]. We decided
to use as model compounds cyclohexanol and hydroxyacetone (acetol, which is formed in some glycerol transfor-
mations). It was intriguing to explore the possibility to accelerate the reaction by visible light irradiation because
oxidation reactions under mild conditions induced by light are attractive from the practical and environmental
points of view, as they open a possibility to use solar energy for stimulating chemical processes. Previously some of
us discovered that alkanes [6] and alcohols [7] can be photo-oxidized by atmospheric oxygen in the presence of
FeCl3. It was also interesting to study a possible effect of addition of pyrazinecarboxylic acid (PCA) [8] on the oxi-
dation reactions.

OH O OH
O O
N COOH
OH
+ CH3 CH3 OH
N
OH hydroxyacetone PCA
cyclohexanol cyclohexanone diol (acetol) acetic acid

2 Experimental/methodology
Catalyst (FeCl3.6H2O) and cocatalyst (PCA) were used in the form of stock solutions in the substrate (oxidized
alcohol) and solvent (acetonitrile), respectively. Hydrogen peroxide (Peróxidos do Brasil, 70% aqueous) was used
in all experiments. The reactions were carried out in acetonitrile solution (total volume 5 mL) under air atmosphere
in a thermostated Pyrex cylindrical vessel at 60 °C. After given time intervals, samples of the reaction solution (0.1
mL) were taken and diluted with acetonitrile up to 1 mL. Triphenylphosphine was added to the samples to quench
the oxidation. The reaction samples were analysed by gas chromatography using a Shimadzu 2010 instrument fitted
with a polyethylene glycol column (INNOWAX, 25 m × 0.2 mm × 0.4 µm) coupled with flame ionization detector
and an automatic injector. Reactions carried out under irradiation were performed in a Pyrex cylindrical vessel sur-
rounded with the thermostated (60 °C) jacket. The full light (λ > 300 nm) of a street fluorescent lamp (500 W) was
used for irradiation.

3 Results and discussion

Tables 1, 2 summarize the results obtained in this preliminary investigation of oxidation of cyclohexanol and
acetol catalyzed by FeCl3. The first catalytic experiments were made in order to evaluate the effect of PCA adding.
In the case of cyclohexanol, the cocatalyst increased the total yield of cyclohexanone and diol from 23 mM to 42
mM (compare Table 1, entries 1, 2). In the presence of PCA, light irradiation accelerates the oxidation (compare
entries 2 and 4). Thus, the best results were obtained for the photooxidation by the system containing PCA (entry
4). In this case turnover number TON attained 560. In the oxidation of acetol, neither addition of PCA nor light
 11th European Congress on Catalysis – EuropaCat-XI, Lyon, France, September 1st-6th, 2013

irradiation had a significant effect. However TON values were high even in the oxidation catalyzed by only iron
chloride (TON = 790; Table 2, entries 2, 3; and TON=850, entry 1). It should be noted that at relatively high con-
centrations of H2O2 (Tables 1, 2, entries 5–7) the yields of oxygenates after 6 h are noteciably lower. It can be due
to over-oxidation of the primary products.

Table 1. Oxidation of cyclohexanol with H2O2 catalyzed by FeCl3 a.

______________________________________________________________________________________________
Entry [H2O2]0 (M) [PCA]0 (mM) Light [Cyclohexanone] (mM) [Diol]b (mM) Initial rate (mM min–1)
_________________________________________________________________________________________________________________________________________________________________________

1 0.5 0 no 12 11 0.16
2 0.5 0.2 no 22 20 0.29
3 0.5 0 yes 20 20 0.23
4 0.5 0.2 yes 25 24 0.44
5 1.0 0 no 6 7 0.08
6 1.5 0 no 7 2 0.03
7 2.0 0 no 2 0.5 0.005
a
Reaction conditions: cyclohexanol, 0.5 M; FeCl3.6H2O, 0.1 mM; H2O2 (70 wt %); acetonitrile up to 5 mL. 60 °C;
6 h. b A mixture of 1,3-cyclohexandiol and 1,4-cyclohexandiol.
______________________________________________________________________________________________

Table 2 Oxidation of hydroxyacetone (acetol) catalyzed by FeCl3 a.

______________________________________________________________________________________________
Entry [H2O2]0 (M) [PCA]0 (mM) Light [Acetic acid] (mM) Initial rate (mM min–1)
__________________________________________________________________________________________________________________________________________________________________________

1 0.5 0 no 85 0.49
2 0.5 0.2 no 79 0.62
3 0.5 0 yes 79 0.41
4 0.5 0.2 yes 82 0.66
5 1.0 0 no 49 0.15
6 1.5 0 no 20 0.08
7 2.0 0 no 17 0.06
a
Reaction conditions: hydroxyacetone, 0.5 M; FeCl3.6H2O, 0.1 mM; H2O2 (70 wt %); acetonitrile up to 5 mL.
60 °C; 6 h.
______________________________________________________________________________________________

4 Conclusions
The simple green salt FeCl3 catalyzes the oxidation of cyclohexanol and hydroxyacetone with hydrogen perox-
ide at 60 °C (TONs attain 850). Addition of PCA and light irradiation improve the reaction.

Acknowledgements
The authors thank UFABC, FAPESP (2011/09362-7) and RFBR (12-03-00084-a) for the support

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