Catal Lett DOI 10.

1007/s10562-009-0103-z

Hydrogen Peroxide Oxygenation of Saturated and Unsaturated Hydrocarbons Catalyzed by Montmorillonite or Aluminum Oxide
Dalmo Mandelli Anielle C. N. do Amaral Yuriy N. Kozlov Lidia S. Shulpina Anderson J. Bonon Wagner A. Carvalho Georgiy B. Shulpin

Received: 9 June 2009 / Accepted: 13 July 2009 Springer Science+Business Media, LLC 2009

Abstract Montmorillonites K-10, Na0.60K0.12Ca0.02(Al1.78 Fe0.12Mg0.10)oct(Si3.89Al0.11)tetO10(OH)2, and NT-25, Na0.10 K0.04Ca0.08(Al1.28Fe0.45Mg0.28)oct(Si3.94Al0.06)tetO10(OH)2, and aluminum oxide, Al2O3, catalyze alkane hydroperoxidation and olen epoxidation with hydrogen peroxide. Alkanes afford alkyl hydroperoxides as main primary products which partially decompose to produce corresponding ketones and alcohols. The oxidation of cis- and trans-isomers of 1,2-dimethylcyclohexane on K-10 proceeds stereoselectively. Benzene in the presence of montmorillonite K-10 is transformed into phenol. Styrene is oxidized to afford benzaldehyde and styrene epoxide. It is proposed on the basis of a kinetic study and measurements of the selectivity parameters that in the case of alumina the oxidation occurs with the participation of
Electronic supplementary material The online version of this article (doi:10.1007/s10562-009-0103-z) contains supplementary material, which is available to authorized users.
D. Mandelli A. C. N. do Amaral A. J. Bonon mica, Pontif cia Universidade Cato lica de Faculdade de Qu Campinas, Campus I, Rod. D. Pedro I, km 136, Pq. das Universidades, Campinas, SP 13086-900, Brazil Y. N. Kozlov G. B. Shulpin (&) Semenov Institute of Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina, dom 4, 119991 Moscow, Russia e-mail: Shulpin@chph.ras.ru; gbsh@mail.ru L. S. Shulpina Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Ulitsa Vavilova, dom 28, 119991 Moscow, Russia W. A. Carvalho ncias Naturais e Humanas, Universidade Federal Centro de Cie , do ABC, Rua Catequese, 242, Bairro Jardim, Santo Andre SP 09090-400, Brazil

hydroxyl radicals generated from an aluminum peroxo derivative on the catalyst surface. In the cases of montmorillonites iron centers are also responsible for the H2O2 activation which gives hydroxyl radicals. Addition of triuoroacetic acid (TFA) leads to the noticeable acceleration of all oxidation reactions and enhancement of the product yield. It has been shown that in the presence of TFA some parts of solid catalysts are transferred into the homogeneous solution. Thus, very cheap natural solid materials provide soluble species that are active in efcient homogeneous oxidations of hydrocarbons with hydrogen peroxide. In the absence of TFA the oxidation reactions in the case of the three catalysts are truly heterogeneous in nature. Keywords Alkanes Alkyl hydroperoxides Aluminum oxide Benzene Heterogeneous catalysis Hydrogen peroxide Montmorillonite Phenol

1 Introduction Hydroxylation and hydroperoxidation of saturated hydrocarbons is one of important goals of contemporary catalytic chemistry. It is known that derivatives of various transition metals efciently catalyze hydrocarbon oxygenation with molecular oxygen and peroxides including cheap and ecologically friendly hydrogen peroxide [16]. It should be emphasized that alkanes are very inert organic compounds and yields in their oxidations are usually low. Yields of around 30% based on the alkane can be considered as high [4, 5]. In the commercial oxidation of cyclohexane by air at 160 C with the participation of Co(II) as a catalyst [6] the desired compounds, cyclohexanol and cyclohexanone, constitute 85% of the products at only 4% conversion.

123

D. Mandelli et al.

These valuable compounds are both also susceptible to further oxidation, and at higher conversion the selectivity will dramatically drop. Solid aluminum-containing compounds, for example, montmorillonites [713], aluminum oxide and some other [1422], are widely used as supports for transition metal complexes which in some cases are efcient catalysts in transformations of organic compounds. Much less is known about reactions of alkanes and olens in solutions catalyzed by compounds of non-transition metals [2329]. For example, alumina has been demonstrated to catalyze olen epoxidation with hydrogen peroxide in ethyl acetate [3038]. Aluminum nitrate has been recently used as a catalyst for olen epoxidation with H2O2 in ethyl acetate as a solvent [39] and alkane hydroperoxidation in acetonitrile [40]. Aluminum derivatives have been used to promote the BaeyerVilliger oxidation [4143]. In the present work, we have found for the rst time that both montmorillonite and aluminum oxide without any additives catalyze oxidation of saturated as well as some unsaturated hydrocarbons.

0.12

0.10

1
Amount / mmol
0.08

0.06

2
0.04

0.02

5 10 15 20 25 30

Time / min
Fig. 1 Accumulation of the products (cyclohexyl hydroperoxide, curve 1; cyclohexanol, curve 2; cyclohexanone, curve 3) in oxidation of cyclohexane (2.7 mmol) with hydrogen peroxide (5.2 mmol) in the presence of montmorillonite K-10 (50 mg) in MeCN at 70 C. Amounts of cyclooctanone and cyclooctanol were determined twice, before and after reduction of the aliquots with solid PPh3 (for this method, see Refs. [5, 44, 45]). Maximum total yield of oxygenates (after 15 min) was 6% based on cyclohexane

2 Results and Discussion In the present work, we studied for the rst time alkane oxidation with H2O2 catalyzed under relatively mild conditions by solid aluminum derivatives (aluminum oxide and montmorillonites). 2.1 Catalysis by Montmorillonites

0.16

Amount / mmol

We have found that montmorillonite K-10, Na0.60K0.12Ca0.02(Al1.78Fe0.12Mg0.10)oct(Si3.89Al0.11)tetO10(OH)2, is a relatively efcient catalyst for oxygenation of alkanes by H2O2 in acetonitrile at 70 or 50 C. The oxidation of cyclohexane and cyclooctane gave mainly the corresponding alkyl hydroperoxides (Figs. 1, 2). Dependences of the initial reaction rate on initial amounts of the catalyst (Fig. 3) and cyclooctane (Fig. 4) have been determined. Addition of water to 70% aqueous hydrogen peroxide leads to some decrease in the initial oxidation rate (determined as the yield after 15 min) and the total yield after 120 min (Table S1). Some non-productive decomposition of hydrogen peroxide to molecular oxygen and water has been noticed (Fig. S3). Selectivity parameters measured for oxidation of various saturated hydrocarbons on the montmorillonite K-10 catalyst are summarized in Table S2 (entry 1). It can be seen that these parameters are close to the values obtained previously [4658] for the oxidations by the systems that operate with the participation of hydroxyl radicals (entries 39) and are different from that obtained for the systems which are believed to operate via other mechanisms (entries 1015). Cyclohexanol under

0.12

0.08

0.04

0 20 40

60 80 100

120

Time / min
Fig. 2 Accumulation of the products (cyclooctyl hydroperoxide, curve 1; cyclooctanol, curve 2; cyclooctanone, curve 3) in oxidation of cyclooctane (2.5 mmol) with hydrogen peroxide (5.0 mmol) in the presence of montmorillonite K-10 (50 mg) in MeCN at 50 C. Amounts of cyclooctanone and cyclooctanol were determined twice, before and after reduction of the aliquots with solid PPh3 (for this method, see Refs. [5, 44, 45]). Maximum total yield of oxygenates (after 120 min) was 6% based on cyclooctane

similar conditions was oxidized to cyclohexanone in yield 17% after 2 h (Fig. S4, curve 1). Cyclooctene was epoxidized in acetonitrile solution at 70 C to afford the epoxide

123

Hydrogen Peroxide Oxygenation of Saturated and Unsaturated Hydrocarbons

0.20

80
1/A3 / M1

2
0.08 0.16

60 40 20 0

Amount / mmol

0.06

0.12

Amount / mmol

0.06

0.04

0.08

Amount / mmol

0.05

0.5

A
0.04

0.02

0.04

0.4

0 0 20 40 60 80 100

0.03

0.3

5
0.2

Amount of montmorillonite / mg

0.02

Fig. 3 Oxidation of cyclooctane (2.5 mmol) with hydrogen peroxide (5.0 mmol) catalyzed by montmorillonite K-10 in MeCN at 50 C. Dependences of total yield of oxygenates after 3 min (mmol; corresponds to the initial rate of oxygenate formation), curve 1, and total amount of oxygenates (mmol) after 120 min (curve 2) on amount of montmorillonite are shown. Amounts of cyclooctanone and cyclooctanol were determined after reduction of the aliquots with solid PPh3. For the original full kinetic curves, see Fig. S1

0.01

0.1

0
0 0 1 2 3 4 5 6 7

Amount of cyclooctane / mmol

Fig. 4 Oxidation of cyclooctane with hydrogen peroxide (5 mmol) catalyzed by montmorillonite K-10 (20 mg) in MeCN at 50 C. Graph A: Dependences of total yield of oxygenates after 3 min (mmol; corresponds to the initial rate of oxygenate formation), curve 1, and total amount of oxygenates (mmol, curve 2, and % based on cyclooctane, curve 3) after 120 min on initial amount of cyclooctane are shown. Amounts of cyclooctanone and cyclooctanol were determined after reduction of the aliquots with solid PPh3. For the original full kinetic curves, see Fig. S2. Graph B: Linearization of dependence 1 using coordinates 1/DA3 - 1/[cyclooctane]0 where DA3 is the concentration (M) of products formed during rst 3 min of the reaction

in yield 21% after 5 h (Fig. S4, curve 2). It is noteworthy that addition of triuoroacetic acid (TFA) in a small amount noticeably accelerates the alkane oxidation and enhances the yield of the oxygenates (Fig. 5). Benzene (0.2 mmol) after heating for 10 h at 70 C with 35% aqueous H2O2 (0.2 mmol), triuoroacetic acid (0.1 mmol), acetonitrile (0.6 mL), and montmorillonite K-10 (20 mg) was transformed into phenol (0.06 mmol, yield 3%). Styrene turned out to be more reactive: heating for 3 h at 70 C a mixture of styrene (1.7 mmol), 35% aqueous H2O2 (0.2 mmol), TFA (0.1 mmol), acetonitrile (0.6 mL), and montmorillonite (20 mg) gave benzaldehyde (0.14 mmol; yield 8.2%), styrene epoxide (0.04 mmol; yield 2.4%), and acetophenone (0.008 mmol; yield 0.5%). The reaction under the same conditions in the absence of TFA gave only benzaldehyde in 2.1% yield. The oxidation by peroxyacetic acid instead of H2O2 afforded benzaldehyde in 3% yield. We have also found that another type of montmorillonite, NT-25, Na0.10K0.04Ca0.08(Al1.28Fe0.45Mg0.28)oct (Si3.94Al0.06)tetO10(OH)2, catalyzes alkane oxidation with hydrogen peroxide. Initial rate of cyclooctane oxygenation and the yield of the oxygenates after 120 min (see Table 1) are ca. 2 times higher than in the reaction with montmorillonite K-10 (see Fig. 2). In order to check if there some leaching of solid catalyst K-10 to the reaction solution we fullled the following experiment. A mixture of K-10 (20 mg), H2O2 (70% aqueous), and acetonitrile (4.7 mL) was stirred at 60 C for

30 min and then the solid catalyst was ltered off at 60 C. Cyclooctane (2.5 mmol) was added to the homogeneous solution and the reaction was continued at 60 C for 3 h. The amount of oxygenates was only 0.0025 mmol (yield 0.1% based on cyclooctane). However, when a mixture of K-10, H2O2, and acetonitrile was incubated for 30 min at 60 C in the presence of TFA (1 mL) yield of oxygenates was 13% after 3 h (Fig. S5, curve 1). It is interesting that when the incubation was in the absence of H2O2 (Fig. S5, curve 2) the yield was even higher (32%). This can be due to some decomposition of H2O2 during incubation period. In another experiment, in the presence of TFA, solid catalyst K-10 was ltered off from the reaction solution after 15 min and the reaction continued further (Fig. S6, Graph A, curve 1). The reaction proceeded exactly as in the experiment without ltering off the catalyst (compare with curve 2 in Fig. S6, Graph A). If TFA is absent the oxidation reaction stops immediately after ltering off the catalyst (Fig. S6, Graph B). Thus, we can conclude that TFA

123

Amount / mmol

4 5 0 1 2 3 1/[cyclooctane]0 / mmol1

% 10

D. Mandelli et al.

2.2 Catalysis by Aluminum Oxide

0.4

Amount / mmol

0.3

0.2

Alumina is less efcient catalyst for the alkane oxidation (compare Figs. 6 and 1). In this case, however, the reaction is more selective: cyclooctyl hydroperoxide is formed as the sole product. The initial rate is proportional to the amount of the catalyst (Fig. 7) and does not depend on the

0.1

1
0.04

0 0 20 40 60 80 100 120

Time / min
Fig. 5 Oxidation of cyclooctane (2.5 mmol) with hydrogen peroxide (5 mmol) catalyzed by montmorillonite K-10 (20 mg) in MeCN at 50 C in the absence (curve 1; yield was 6.4% after 120 min) and in the presence of triuoroacetic acid (0.044 g; curve 2; yield was 15.3% after 120 min). Total amounts of oxygenates (cyclooctanol ? cyclooctanone) are shown. Amounts of cyclooctanone and cyclooctanol were determined after reduction of the aliquots with solid PPh3

Amount / mmol

0.03

0.02

1
0.01

0 0 60 120 180 240 300 360

Time / min
Table 1 Oxidation of cyclooctane with H2O2 catalyzed by montmorillonite NT-25 Time (min) 1 2 3 15 60 120 Cyclooctanone (mmol) 0 0 0 0 0.03 0.04 Cyclooctanol (mmol) 0.025 0.047 0.061 0.16 0.22 0.24 Yield (based on cyclooctane; %) 0.9 1.7 2.3 5.9 9.3 10.4
0.025 0.030

Fig. 6 Accumulation of cyclooctyl hydroperoxide, in the oxidation of cyclooctane (2.5 mmol) with hydrogen peroxide (5.0 mmol) in the absence (curve 1) and in the presence of aluminum oxide (100 mg; curve 2) in MeCN at 80 C. Amounts of cyclooctanone and cyclooctanol were determined twice, before and after reduction of the aliquots with solid PPh3 (for this method, see Refs. [5, 44, 45])

Amount / mmol

Conditions Cyclooctane, 2.7 mmol; H2O2, 5.7 mmol; montmorillonite NT-25, 20 mg; acetonitrile, up to 5 mL; 50 C. Concentrations of the products were measured after reduction with PPh3

0.020

0.015 2

extracts soluble catalytically active (most probably ironcontaining) species from K-10 and NT-25 into the homogeneous solution. In the absence of TFA the catalytic reaction is truly heterogeneous in nature. Some loss of activity upon catalyst recycling has been found only for the second cycle. Thus, in the cyclooctane oxidation (the reaction at 70 C; for other conditions, see caption to Fig. S6) with fresh sample of K-10 the yield of oxygenates was 13% based on cyclooctane after 1 h. The catalyst was ltered off, washed with acetonitrile and dried in air (70 C, 4 h). The yield of oxygenates was 5.9%. It is noteworthy, however, that the third, fourth and fth cycles gave the same yields: 5.4, 6.0, and 5.3%, respectively. Thus, the catalyst can be easily isolated from the reaction mixture and re-used many times without loss of activity.

0.010

0.08

0.005

100 200

300 400

0.04 0 500

Amount of aluminum oxide / mg

Fig. 7 Oxidation of cyclooctane (2.5 mmol) with hydrogen peroxide (5.0 mmol) catalyzed by aluminum oxide in MeCN at 80 C. Dependences of total yield of oxygenates after 30 min (mmol; corresponds to the initial rate of oxygenate formation), curve 1, and total amount of oxygenates (mmol) after 300 min (curve 2) on amount of aluminum oxide are shown. Amounts of cyclooctanone and cyclooctanol were determined after reduction of the aliquots with solid PPh3. For the original full kinetic curves, see Fig. S8

123

Amount / mmol

Hydrogen Peroxide Oxygenation of Saturated and Unsaturated Hydrocarbons

500 1/A15 / M1 400 300 200 100 0

B
Amount / mmol

0.008

0.006

0.004

0.08

2
0.002

0.012

10

1/[cyclooctane]0 / mmol1

% 2 0.05 0.04
0

0.010

0.04

Amount / mmol

0.008

Amount / mmol

2 3 0 1

Amount of H2O2 / mmol

Fig. 9 Oxidation of cyclooctane (3.5 mmol) with hydrogen peroxide catalyzed by aluminum oxide (100 mg) in MeCN at 80 C. Dependences of total yield of oxygenates after 15 min (mmol; corresponds to the initial rate of oxygenate formation), curve 1, and total amount of oxygenates (mmol, curve 2) after 300 min on initial amount of hydrogen peroxide are shown. Amounts of cyclooctanone and cyclooctanol were determined after reduction of the aliquots with solid PPh3. For the original full kinetic curves, see Fig. S10

0.006

0.03

0.004

0.02

0.002

0.01 0

0 0 1 2 3 4 5

Amount of cyclooctane / mmol

Fig. 8 Oxidation of cyclooctane with hydrogen peroxide (5 mmol) catalyzed by aluminum oxide (100 mg) in MeCN at 80 C. Graph A: Dependences of total yield of oxygenates after 15 min (mmol; corresponds to the initial rate of oxygenate formation), curve 1, and total amount of oxygenates (mmol, curve 2, and % based on cyclooctane, curve 3) after 300 min on initial amount of cyclooctane are shown. Amounts of cyclooctanone and cyclooctanol were determined after reduction of the aliquots with solid PPh3. For the original full kinetic curves, see Fig. S9. Graph B: Linearization of dependence 1 using coordinates 1/DA15 - 1/[cyclooctane]0 where DA15 is the concentration (M) of oxygenates formed during rst 15 min of the reaction

0 .2 0

Amount / mmol

0 .1 5

0 .1 0

1
0 .0 5

0 0 60 120 180 240 300 360

Time / min

amount of cyclooctane at its amount [3 mmol (Fig. 8). Similarly, the W0 value does not depend on the amount of H2O2 in the interval 28 mmol (Fig. 9). The selectivity parameters in this case are also low (Table S2, entry 2). The reaction is accelerated if triuoroacetic acid is added in low concentration (Fig. 10). In the leaching experiments, a mixture of alumina, hydrogen peroxide and acetonitrile was incubated for 2 h. After that the solid catalyst was ltered off at 80 C, cyclooctane and additional amount of H2O2 was added and the homogeneous solution and the reaction continued for additional 5 h the yield of the oxygenates was only 1% (Fig. S11, curve 1). When the incubation was performed in the presence of TFA the oxidation occurred even in the absence of the solid alumina (Fig. S11, curve 2) giving the oxygenates in 12% yield after 5 h.

Fig. 10 Accumulation of cyclooctyl hydroperoxide in the oxidation of cyclooctane (2.5 mmol) with hydrogen peroxide (5 mmol) catalyzed by aluminum oxide (100 mg) in MeCN at 80 C in the absence (curve 1; yield was 1.2% after 300 min) and in the presence of triuoroacetic acid (0.044 g; curve 2; yield was 7.2% after 300 min). Amounts of cyclooctanone and cyclooctanol were determined twice, before and after reduction of the aliquots with solid PPh3 (for this method, see Refs. [5, 44, 45])

2.3 Mechanistic Consideration The experimental data discussed above and the selectivity parameters summarized in Table S2 indicate that both systems, H2O2/montmorillonite and H2O2/aluminum oxide, generate hydroxyl radicals which induce the hydrocarbon oxygenation. The results of kinetic study (the dependences of the initial reaction rates on the initial

123

Amount / mmol

D. Mandelli et al.

amount of the alkane) presented in Figs. 4 and 8 are in a good agreement with this proposal. The shapes of these kinetic dependences for both systems are typical for the case of competition between the alkane and (most probably) acetonitrile for the same oxidizing species which is hydroxyl radical. This competition can be described by the following simple kinetic scheme of the process: H2 O2 =catalyst ! HO HO MeCN ! products HO RH ! R H2 O ROO e H ! ROOH
  

The dependence of the initial reaction rate on initial concentration of hydrogen peroxide for the catalysis by aluminum oxide allowed us to roughly analyze the model which involves the formation of an intermediate peroxo derivative on the surface of alumina particles. We conventionally denote this peroxo derivative as (Al2O3H2O2)S: H2 O2 Al2 O3 S ) Al2 O3 H2 O2 0S Al2 O3 H2 O2 0S ! Al2 O3 S 2HO K5 5 6

Wi k1 k2

i 1 2 3

where Wi is the rate of the oxidizing species generation by the H2O2/catalyst system. Acetonitrile is oxidized in accord with Eq. 1 to afford formaldehyde, formic acid and CO2 [46]. The analysis of the scheme given above in the steadystate approximation relative to hydroxyl radicals gave the following equation for oxidation rate W of cyclooctane, RH: W dRH dROOH Wi k1 MeCN dt dt 1 k RH 2 4

In the frames of this proposal, the change in the alkane oxidation rate is due to the change of the relative amount of species (Al2O3H2O2)S that is the portion of alumina surface H(H2O2) occupied by the peroxo derivative. We can easily obtain in the quasi-equilibrium approximation the following equation: HH2 O2 K5 H2 O2 1 K5 H2 O2 7

The experimental data shown in Figs. 4 and 8 can be described by Eq. 4 because satisfactory linear depen1 dences of W-1 on [cyclooctane]have been obtained 0 (see Graphs B in Figs. 4, 8) in accord with Eq. 4. We accepted in these calculations that W = (DA3 9 200)/ (3 9 60) M s-1 for the montmorillonite-catalyzed oxidation and W = (DA15 9 200)/(15 9 60) M s-1 for the case of aluminum oxide, where DA3 and DA15 are the amounts of oxygenates produced during the rst 3 or 15 min, respectively. It follows from these linear dependences that under conditions described in captions to Figs. 4 and 8 the rates of active species generation Wi are equal to 8.5 9 10-5 and 4.4 9 10-6 M s-1 for montmorillonite K-10 and aluminum oxide, respectively. The k1[MeCN]/k2 ratios were calculated to be 0.82 M for montmorillonite K-10 at 50 C and 0.78 M for aluminum oxide at 80 C. The values of the k1[MeCN]/k2 ratio for both heterogeneous catalysts as well as for soluble aluminum nitrate [40] are close and this supports our kinetic model. At once the hydroxyl radical generation rates Wi differ sufciently for these catalysts (Table 2).
Table 2 Kinetic parameters for the cyclooctane oxidation with H2O2 catalyzed by aluminum-containing compounds Catalyst Montmorillonite K-10 at 50 C Aluminum oxide at 80 C Al(NO3)3 at 70 C k1[MeCN]/k2 (M) 0.82 0.78 0.83 106 9 Wi (M s-1) 17 4.4 7.5

From Eq. 1 = K5[H2O2] we derive the condition when the reaction rate is equal to the half of the maximum possible. It follows from the data of Fig. 9 that the value Wi = Wmax is attained at [H2O2] & 0.2 M, and it means that K5 & 5 M-1. As alumina samples used in the oxidations contained only trace amounts of transition metals (Fe \ 0.01%) we can propose that in the case of alumina hydroxyl radicals are generated with the participation of an aluminum peroxo derivative [59] although the mechanistic details are not clear. The hydroxyl radicals attack the alkane to generate the alkyl radical, R, which rapidly reacts with molecular oxygen: R ? O2 ? ROO. The reduction of the alkylperoxyl radical leads to the formation the main primary product of the reaction, alkyl hydroperoxide: ROO ? H? ? e- ? ROOH. Compounds containing double bonds are epoxidized by the peroxo aluminum fragment: Olen ? AlOOH ? Olen epoxide ? AlOH. It should be noted that many details of this mechanism are still unclear. Oxidations with the participation of montmorillonites proceed noticeably faster than in the case of alumina. As both used montmorillonites contain sufcient amounts of iron it is reasonable to assume that iron ions are responsible for the generation of hydroxyl radicals in this case. Highvalent ions can be reduced by hydrogen peroxide: Fe(III) ? H2O2 ? Fe(II) ? HOO ? H?. Low-valent iron reacts with the second H2O2 molecule producing hydroxyl radicals: Fe(II) ? H2O2 ? Fe(III) ? HO- ? HO. The reaction with montmorillonite K-10 exhibits some stereoselectivity: predominant formation of the alcohol with cis-orientation of the methyl groups (the trans/cis ratio is 0.6) is noticed in the case of oxidation of

123

Hydrogen Peroxide Oxygenation of Saturated and Unsaturated Hydrocarbons

1.0

2
1.5

logW 0 (mmol min1)

low concentration of iron ions in the solution. The solid catalyst permanently feeds the reaction solution with catalytically active iron ions. Evidently, the systems based on very cheap montmorillonites can be used in industrial oxidation of alkanes and other compounds.

2.0 2.5 3.0 3.5

2.9 3.0 3.1 3.2 3.3

4 Experimental The chemical composition of montmorillonite K-10 (Fluka) was determined by X-Ray Fluorescence analysis (spectrometer Philips, model PW2404): 65.34% SiO2, 12.89% Al2O3, 2.38% Fe2O3, 0.95% MgO, 0.52% TiO2, 0.24% CaO, 0.53% Na2O, 1.54% K2O, 7.85% P2O5. Loss on ignition (LOI) was calculated from the difference in weight before and after burning at 1,050 C of a sample previously dried at 110 C (in order to remove remaining moisture). LOI (loss on ignition at 1,050 K) was 8.06%. For the BET surface area determination a Micrometrics ASAP 2010 device was used to make adsorption-desorption measurements at -196 C, under pressure ranging from 10 to 925 mm Hg. Before each measurement the samples were outgassed at 150 C and 1.3 9 10-3 Pa for 12 h. Specic area was 232 m2 g-1. The formula of one half unit cell is Na0.60K0.12Ca0.02(Al1.78Fe0.12Mg0.10)oct (Si3.89Al0.11)tetO10(OH)2. In this formula, Fe2?, Mg2? and Al3? are the isomorphically substituting cations, and Na?, K? and Ca2? are the charge-compensating cations. The symbols oct and tet are related to the octahedral and tetrahedral layers, respectively (see Fig. S12 [69]). Based on the quantity of charge-compensating cations, the theoretical cation exchange capacity (CEC = 1.9 meq g-1) was calculated. The experimental cation exchange capacity, CECexp = 0.451 meq g-1 [70], of the original clay was determined by the Cu-ethylenediamine method [71]. Scanning Electron Microscopy (the Leica-Zeiss microscope LEO 440i coupled in an energy dispersive analyzer of Si(Li) with Be window, Oxford 7060) showed (Fig. S13) that the material contained some amount of large ([2 lm) particles, which were removed by decantation. The bentonite clay mineral containing montmorillonite o Nordeste NT-25 as the main constituent (Bentonit Unia ba State, S.A.) is originated from Campina Grande, Para Brazil. The chemical composition obtained by X-Ray Fluorescence analysis is 57.85% SiO2, 16.74% Al2O3, 8.78% Fe2O3, 2.73% MgO, 1.24% TiO2, 1.08% CaO, 0.73% Na2O, 0.43% K2O, 0.27% P2O5, and 10.10% LOI. The formula of one half unit cell is Na0.10K0.04Ca0.08(Al1.28Fe0.45Mg0.28)oct(Si3.94Al0.06)tetO10(OH)2 with a theoretical cation exchange capacity CEC = 0.8 meq g-1. The BET surface area is 139 m2 g-1. Diffractograms of the two montmorillonites (a Shimadzu model XD-3A diffractometer, with Cu Ka radiation; spectra were

1000 / K1 T
Fig. 11 Arrhenius dependences of logW0 on 1/T for the cyclooctane oxidations catalyzed by NT-25 (1) and K-10 (2) in the presence of CF3COOH

cis-1,2-DMCH. The oxidation of trans-1,2-DMCH gave rise to the prevalence of the trans-alcohol (the trans/cis ratio is 1.5). Oxidation reactions on mono- and polynuclear iron centers in soluble [60, 61] and solid [7, 62] compounds are well-known. In some cases reactions catalyzed by compounds of iron and other transition-metals proceed stereoselectively [6366]. The activation energy Ea value measured (Fig. 11) for NT-25 (20 3) is lower than that for K-10 (26 6 kcal mol-1).

3 Conclusions In the present work, the rst example of alkane oxidation with H2O2 catalyzed by a solid non-transition metal derivative (aluminum oxide) is described. The experimental data indicate that in catalysis by montmorillonites, there are iron ions which are responsible for the generation of hydroxyl radicals from H2O2. The oxidation reactions are truly heterogeneous in nature. It is known that stoichiometric Fenton reagent (H2O2 ? FeII) and Fenton-type catalytic systems containing FeIII ions [67, 68] in the absence of N-ligands are not efcient in alkane oxidations (low yields, tar formation, high catalase activity). In contrast, our systems which use natural iron-containing montmorillonites allow us to oxidize alkanes very efciently in the presence of a small amount of TFA: the product yields attain 32%, alkyl hydroperoxides are formed as predominant products, hydrogen peroxide is not decomposed non-productively to O2 and H2O. Such a gentle behavior of the systems can be due to permanently

123

D. Mandelli et al.

registered between 2h = 2 and 40, with scanning speed of 2 h min-1, using a cathode current of 25 mA and a voltage of 35 kV) are shown in Fig. S14. Size particle distributions of the samples of K-10 and NT-25 are shown in Figs. S15 and S16, respectively. For particle size distribution analysis, two different kinds of techniques were employed: a laser diffraction and image method. The laser diffraction analyses (in triplicate) were carried out on the HORIBA LA-950 instrument; water was used as dispersion medium, the circulation speed was 5 at 95.3% of transmittance without ultrasonic bath. The Portable FlowCAM VS.I (Fluid Imaging Technologies) instrument was used for image particle analysis; water was used as dispersion medium, with 109 optical amplication lens and 300 lm owcell. Photos of samples (shown in the left sides of Figs. S15, S16) demonstrate that there is no particle agglomerations. Alumina (Fluka, type 507C, neutral, 100125 mesh, pH = 7) was used. The surface area, obtained by BET (Micrometrics ASAP 2010 instrument with nitrogen as probe molecule), was 150 m2 g-1, and the average pore size was 5.8 nm. X-ray diffraction (Shimadzu XD-3A diffractometer) showed a Bohemite structure. Size particle distribution of the samples is shown in Fig. S17. Photos of samples (shown in the left side of Fig. S17) demonstrate that there is no particle agglomerations. Energy dispersive X-ray analysis (EDX, Philips CM30T electron microscope with an LaB6 lament) showed that the Al2O3 only contained traces of Si, Cl, Fe and S (\0.01%). Typically, alumina was calcined prior the oxidation reaction by heating at 500 C during 16 h. The oxidations of hydrocarbons in acetonitrile were carried out in air in thermostated Pyrex cylindrical vessels with vigorous stirring. Hydrogen peroxide (usually 70% xidos do Brasil) was used as received. The aqueous; Pero total volume of the reaction solution was usually 5 mL. Typically, the reaction started when the hydrogen peroxide was added in one portion to the solution of the substrate and the catalyst in MeCN. (CAUTION: the combination of air and H2O2 with organic compounds at elevated temperatures may be explosive!). In the case of alkanes, samples of the reaction solutions were analyzed by GC. The oxygenation of alkanes gives rise to the formation of the corresponding alkyl hydroperoxides as the main product. To demonstrate the formation of alkyl hydroperoxides during this oxidation and to estimate its concentration in the course of the reaction, we used a simple method developed earlier by some of us [5, 44, 45]. In the kinetic study of the cycloctane oxidation, we measured the concentrations of cyclooctanone and cyclooctanol only after reduction with PPh3, because this reduction gives the most precise values of total concentration of the products. Other details are given in Figure captions. Concentrations of

products obtained in the oxidation of benzene and styrene by 35% aqueous H2O2 were measured using 1H NMR method (solutions in acetone-d6; Bruker AMX-400 instrument, 400 MHz), signals were integrated using added 1,4-dinitrobenzene as a standard.
o Acknowledgments This work was supported by the State of Sa o de Amparo a Pesquisa do Paulo Research Foundation (Fundac a o Paulo, FAPESP; grants Nos. 2005/51579-2, 2006/ Estado de Sa 03996-6), the Brazilian National Council on Scientic and Technological Development (Conselho Nacional de Desenvolvimento gico, CNPq, Brazil; grants Nos. 478165/2006-4, Cientico e Tecnolo 305014/2007-2) and the Russian Foundation for Basic Research tica (grant No. 06-03-32344-a). The authors thank the Radchrom Anal for help in particle size distribution analysis, Mr. Rafael Bogarin and Miss Cristhiane Capelazzo for their help in the experiments. L. S. S. and G. B. S. express their gratitude to the FAPESP (grant No. 2006/ 03984-8), the CNPq (grant No. 300601/01-8), and the Faculdade de mica, Pontif cia Universidade Cato lica de Campinas for making it Qu possible for them to stay at this University as invited scientists and to perform a part of the present work.

References
1. Strukul G (ed) (1992) Catalytic oxidations with hydrogen peroxide as oxidant. Kluwer, Dordrecht 2. Shilov AE, Shulpin GB (1997) Chem Rev 97:28792932 3. Shilov AE, Shulpin GB (2000) Activation and catalytic reactions of saturated hydrocarbons in the presence of metal complexes. Kluwer, Dordrecht 4. Shulpin GB (2004) Oxidations of CH compounds catalyzed by metal complexes. In: Beller M, Bolm C (eds) Transition metals for organic synthesis, vol 2, 2nd edn. WileyVCH, Weinheim, pp 215242 5. Shulpin GB (2009) Mini-Rev Org Chem (Bentham) 6:95104 6. Ingold KU (1989) Aldrichim Acta 22:6974 7. Pillai UR, Sahle-Demessie E (2003) Appl Catal A: General 245:103109 8. Kaneda K, Ebitani K, Mizugaki T, Mori K (2006) Bull Chem Soc Jpn 79:9811016 9. Mitsudome T, Nosaka N, Mori K, Mizugaki T, Ebitani K, Kaneda K (2005) Chem Lett 34:16261629 10. Anisia KS, Kumar A (2007) J Mol Catal A: Chem 271:164179 11. Rezala H, Khalaf H, Valverde JL, Romaro A, Molinari A, Maldotti A (2009) Appl Catal A: Gen 352:234242 12. Khedher I, Ghorbel A, Fraile JM, Mayoral JA (2009) CR Chimie 12:787792 13. Ben Achma R, Ghorbel A, Sayadi S, Danov A, Medina F (2008) J Phys Chem Solids 69:11161120 14. Shimura K, Fujita K, Kanaia H, Utani K, Imamura S (2004) Appl Catal A: Gen 274:253257 15. Patil NS, Jha R, Uphade BS, Bhargava SK, Choudhary VR (2004) Appl Catal A: Gen 275:8793 16. Salavati-Niasari M, Elzami MR, Mansournia MR, Hydarzadeh S (2004) J Mol Catal A: Chem 221:169175 17. Li CR, Feng YS, Yang QH (2006) Progr Chem 18:14821488 18. Salavati-Niasari M, Amiri A (2005) Appl Catal A: Gen 290: 4653 19. Yin D, Qin L, Liu J, Li C, Jin Y (2005) J Mol Catal A: Chem 240:4048 20. Krumpelt M, Rossignol C, Liu D-J (2008) 124:1317

123

Hydrogen Peroxide Oxygenation of Saturated and Unsaturated Hydrocarbons 21. Ookawa M, Takata Y, Suzuki M, Inukai K, Maekawa T, Yamaguchi T (2008) 34:679685 22. Luo M, Bowden D, Brimblecombe P (2009) Appl Catal B: Environ 85:201206 23. Hirano M, Oose M, Morimoto T (1991) Bull Chem Soc Jpn 64:10461047 24. Hirano M, Oose M, Morimoto T (1991) Chem Lett 331332 25. Greenhalgh RP (1992) Synlett 235236 26. Hirano M, Yakabe S, Clark JH, Kudo H, Morimoto T (1996) Synth Commun 26:18751886 27. Wang H-L, Li R, Zheng Y-F, Chen H-N, Jin J, Wang F-S, Ma J-T (2007) Helv Chim Acta 90:18371847 28. Pescarmona PP, Janssen KPF, Jacobs PA (2007) Chem Eur J 13:65626572 29. Pescarmona PP, Jacobs PA (2008) Catal Today 137:5260 30. Rebek J, McCready R (1979) Tetrahedron Lett 45:43374338 31. van Vliet MCA, Mandelli D, Arends IWCE, Schuchardt U, Sheldon RA (2001) Green Chem 3:243246 32. Mandelli D, van Vliet MCA, Sheldon RA, Schuchardt U (2001) Appl Catal A 219:209213 33. Cesquini RG, Silva JMS, Woitiski CB, Mandelli D, Rinaldi R, Schuchardt U (2002) Adv Synth Catal 344:911914 34. Rinaldi R, Sepulveda J, Schuchardt U (2004) Adv Synth Catal 346:281285 35. Rinaldi R, Schuchardt U (2004) J Catal 227:109116 36. Rinaldi R, Schuchardt U (2005) J Catal 236:335345 37. Silva JMS, Vinhado FS, Mandelli D, Schuchardt U, Rinaldi R (2006) J Mol Catal A: Chem 252:186193 38. Rinaldi R, Schuchardt U (2006) J Catal 236:335345 39. Rinaldi R, Fujiwara FY, Schuchardt U (2004) Catal Commun 5:333337 40. Mandelli D, Chiacchio KC, Kozlov YN, Shulpin GB (2008) Tetrahedron Lett 49:66936697 41. Frison J-C, Palazzi C, Bolm C (2006) 62:67006706 42. Steffen RA, Teixeira S, Sepulveda J, Rinaldi R, Schuchardt U (2008) J Mol Catal A: Chem 287:4144 43. Lei Z, Ma G, Wei L, Yang Q, Su B (2008) Catal Lett 124:330 333 44. Shulpin GB (2002) J Mol Catal A: Chem 189:3966 45. Shulpin GB (2003) CR Chimie 6:163178 ss-Fink G, Nizova GV, Stanislas S, Shulpin GB (1998) J Mol 46. Su Catal A: Chem 130:163170 47. Kozlov YN, Nizova GV, Shulpin GB (2005) J Mol Catal A: Chem 227:247253 48. Shulpin GB, Mishra GS, Shulpina LS, Strelkova TV, Pombeiro AJL (2007) Catal Commun 8:15161520 P, Su ss49. Kozlov YN, Romakh VB, Kitaygorodskiy A, Buglyo Fink G, Shulpin GB (2007) J Phys Chem A 111:77367752 50. Shulpin GB (2002) J Chem Res (S) 35:1353 51. Shulpin GB, Kudinov AR, Shulpina LS, Petrovskaya EA (2006) J Organomet Chem 691:837845 52. Shulpin GB, Kirillova MV, Sooknoi T, Pombeiro AJL (2008) Catal Lett 123:135141 ss-Fink G, Shulpina 53. Shulpin GB, Sooknoi T, Romakh VB, Su LS (2006) Tetrahedron Lett 47:30713075 ss-Fink G, Shulpina LS (2001) J Mol Catal A: 54. Shulpin GB, Su Chem 170:1734 55. Woitiski CB, Kozlov YN, Mandelli D, Nizova GV, Schuchardt U, Shulpin GB (2004) J Mol Catal A: Chem 222:103119 56. dos Santos VA, Shulpina LS, Veghini D, Mandelli D, Shulpin GB (2006) React Kinet Catal Lett 88:339348 ss-Fink G, Shulpin GB (2007) Inorg 57. Romakh VB, Therrien B, Su Chem 46:13151331 58. Shulpin GB, Matthes MG, Romakh VB, Barbosa MIF, Aoyagi JLT, Mandelli D (2008) Tetrahedron 64:21432152 59. Lefer JE, Miller DW (1977) J Am Chem Soc 99:480483 ss-Fink G, Schindler S, Westerheide L, 60. Nizova GV, Krebs B, Su Gonzalez Cuervo L, Shulpin GB (2002) Tetrahedron 58:9231 9237 ss-Fink G, Shulpin GB (2007) Inorg 61. Romakh VB, Therrien B, Su Chem 46:31663175 62. Ivanov AA, Chernyavsky VS, Gross MJ, Kharitonov AS, Uriarte AK, Panov GI (2003) Appl Catal A: General 249:327343 63. Chen K, Que L Jr (2001) J Am Chem Soc 123:63276337 64. Groves JT (2006) J Inorg Biochem 100:434447 65. Yiu S-M, Man W-L, Lau T-C (2008) J Am Chem Soc 130:1082110827 66. Shteinman AA (2008) Uspekhi Khimii 77:10131035 (in Russian) ss67. Shulpin GB, Nizova GV, Kozlov YN, Gonzalez Cuervo L, Su Fink G (2004) Adv Synth Catal 346:317332 ss-Fink G, Shulpina LS, Mandelli 68. Shulpin GB, Golfeto CC, Su D (2005) Tetrahedron Lett 46:45634567 gono/ 69. Krauskopf KB (1972) Introduction to geochemistry. Pol o Paulo (in Portuguese) EDUSP, Sa 70. Dal Bosco SM, Jimenez RS, Vignado C, Fontana J, Geraldo B, Figueiredo FCA, Mandelli D, Carvalho WA (2006) Adsorption 12:133146 71. Bergaya F, Vayer M (1997) Appl Clay Sci 12:275280

123