Oxidation of alcohols to aldehydes and ketones using TBHP as an oxidant over LaMO3 (M = Cr, Mn, Co, Ni, Fe) perovskites

Article abstract of DOI:10.1080/00397911.2010.520401

Oxidation of a wide variety of structurally and electronically diverse primary and secondary alcohols to aldehydes and ketones was carried out using a novel catalytic system of LaCrO₃ and tert-butyl hydroperoxide (TBHP) under solvent-free conditions. The methodology afforded the desired carbonyl compounds in good to excellent yields, and the catalyst can be reused several times with no significant loss in activity. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397911.2010.520401

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Oxidation of Alcohols to Aldehydes
and Ketones Using TBHP as an Oxidant
over LaMO3 (M ˭ Cr, Mn, Co, Ni, Fe)
Perovskites
Savita J. Singh a & Radha V. Jayaram a
a Department of Chemistry, Institute of Chemical Technology,
Mumbai, India
Accepted author version posted online: 30 Jun 2011.Version of
record first published: 06 Oct 2011.
To cite this article: Savita J. Singh & Radha V. Jayaram (2012): Oxidation of Alcohols to Aldehydes
and Ketones Using TBHP as an Oxidant over LaMO3 (M ˭ Cr, Mn, Co, Ni, Fe) Perovskites, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
42:3, 299-308
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Synthetic Communications1, 42: 299–308, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2010.520401
OXIDATION OF ALCOHOLS TO ALDEHYDES AND
KETONES USING TBHP AS AN OXIDANT OVER LaMO3
=
(M Cr, Mn, Co, Ni, Fe) PEROVSKITES
Savita J. Singh and Radha V. Jayaram
Department of Chemistry, Institute of Chemical Technology, Mumbai, India
GRAPHICAL ABSTRACT
Abstract Oxidation of a wide variety of structurally and electronically diverse primary and
secondary alcohols to aldehydes and ketones was carried out using a novel catalytic system
of LaCrO3 and tert-butyl hydroperoxide (TBHP) under solvent-free conditions. The
methodology afforded the desired carbonyl compounds in good to excellent yields, and
the catalyst can be reused several times with no significant loss in activity.
Keywords Alcohol oxidation; carbonyl compounds; perovskite catalyst
INTRODUCTION
Oxidation of alcohols to aldehydes and ketones is one of the fundamental and
most desirable chemical transformation in organic synthesis in view of the fact that
aldehydes and ketones serve as starting materials for a multitude of other reactions,
but these compounds do not have the same broad commercial availability or stability
of alcohols.[1] Traditionally, this transformation is performed with a stoichiometric
amount of chromium- or manganese-based toxic reagents in combination with vol-
atile, hazardous, and flammable solvents.[2] In these methods, purification of the
reaction product is often demanding and laborious. Because of the industrial impor-
tance of this reaction and also the diffusion of green chemistry throughout the syn-
thetic processes, the development of effective, greener catalytic systems that use
less-hazardous oxidants is an important challenge in this field. Over the past several
Received February 5, 2010.
Address correspondence to Radha V. Jayaram, Department of Chemistry, Institute of Chemical
Technology, N. Parekh Marg, Matunga, Mumbai 400 019, India. E-mail: rv.jayaram@ictmumbai.edu.in
299

300
S. J. SINGH AND R. V. JAYARAM
years, the stoichiometric reagents for this reaction are gradually replaced by various
catalytic systems, and many homogeneous and heterogeneous catalytic systems such
as RuCl3=(diacetoxyiodo)benzene,[3a] RuCl2(PPh3)3=TEMPO,[3b] Pd(OAc)2,[3c]
NHPI=vanadium cocatalysts,[3d] palladium(II) bathophenanthroline,[3e] CuCl2=tet-
rabutylammonium bromide,[3f] Co(OAc)2=NHPI,[3g] HNO3=Br2,[3h] FeBr3,[3i]
PDC=Adogen 464,[3j] Zr(OtBu)4,[3k] hydrotalcite-supported Pd(OAc)2=pyridine,[3l]
silica-supported Ru complex,[3m] Mo-V-O oxide,[3n] Bi-Pd=Al2O3,[3o] Au=TiO2,[3p]
[Mn(bpy)2]2þ=HMS,[3q] Co(II)=ZnO,[3r] Fe3þ=mont-K10,[3s] PEEKWC microcapsul-
es,[3t] Cr(salen)=MCM-41,[3u] CrO3,[3v] CrS-2,[3w] PIPO,[3b] Bi=BEA and Bi=
ZSM-5,[3x] and silica gel–supported zirconium catalyst[3k] have been developed to
effect this transformation.
A gamut of oxides crystallizing in perovskite-related structures have proved
to be attractive and potential catalysts in the past as far as vapor-phase oxidation
reactions[4a–e] are concerned because of their robust structure, varied physico-
chemical properties, nontoxicity, ease of handling, and stability at very high tem-
peratures.[5] However, liquid-phase heterogeneous catalysis of them is still a fertile
area of research. The activity of these perovskite catalysts surpasses that of the
binary oxides because of their greater chemical stability and structural rigidity,
and there is always a scope to extend their oxidizing potential to liquid-phase reac-
tions. In a time of growing need for green catalysts, because of their high metal
content and high resistance to dissolution in aqueous=organic solvents and in
acidic and basic media, perovskites have been rediscovered as heterogeneous
catalysts of great diversity and versatility for liquid-phase organic reactions.
In the past 7–8 years, use of perovskite-type heterogeneous catalysts for
liquid-phase reactions has gained interest, and they have been used as efficient cata-
lysts for a few liquid-phase organic reactions (catalytic transfer hydrogenation,[6a,b]
Ullmann and Sonogashira reactions,[7] Suzuki couplings,[8] O-Boc protection of
hydroxy compounds,[9] and acetylation of amines, alcohols, and phenols[10]).
Recently, in a study, we have utilized the oxidizing potential of perovskites in
combination with tert-butyl hydroperoxide (TBHP) for oxidative fuctionalization of
alkylarenes to phenyl ketones, which are valuable building blocks for the manufac-
ture of several speciality chemicals.[11] In the present work, we have extended the
=
catalytic application of LaMO3 (M Cr, Co, Fe, Mn, Ni) perovskites in organic syn-
thesis for the selective oxidation of alcohols to aldehydes and ketones using TBHP
under solvent-free conditions (Scheme 1).
Scheme 1. Oxidation of primary and secondary alcohols over LaCrO3 perovskite.

OXIDATION OF ALCOHOLS OVER PEROVSKITES
301
Table 1. Oxidation of 1-phenyl ethanol over LaMO3 perovskitesa
Entry
Oxide
Yieldb (%)
1
2
3
4
5
6
7
LaCrO3
LaMnO3
LaCoO3
LaNiO3
LaFeO3
Cr2O3
97
84
81
70
68
40
27
La2O3
aReaction conditions: 1-phenyl ethanol ¼ 1 mmol, 70% TBHP ¼ 0.129 g (1 mmol
equivalent of TBHP), oxide ¼ 10 mol %, time ¼ 0.5 h, temperature ¼ 90 ꢀC.
bYield determined by GC and GCMS analysis.
RESULTS AND DISCUSSION
In the present work, we have investigated the oxidation of 1-phenyl ethanol
with TBHP in the presence of a catalytic amount of the LaMO3 perovskites under
solvent-free conditions (Table 1, entries 1–5). Among all the perovskites (viz.,
LaCrO3, LaMnO3, LaCoO3, LaNiO3, and LaFeO3), the activity of LaCrO3 was
found to be superior, and hence it was chosen for further studies. The catalytic
activities of the component oxides of LaCrO3 (La2O3 and Cr2O3) were also tested
for the reaction, but the results were not as good as those obtained for the
perovskite-catalyzed reaction (Table 1, entries 6 and 7).
The oxidation of 1-phenyl ethanol with TBHP can be driven to 97% yield in
favor of acetophenone by using 10 mol% LaCrO3 and heating the reaction mixture
for 0.5 h at 90 ꢀC (Table 2, entry 1), whereas when this reaction was performed in
the absence of TBHP no formation of acetophenone was observed (Table 2, entry
2). An experiment without the catalyst using the same reaction conditions did not
yield the oxidation product (Table 2, entry 3). In an effort to evolve the optimum
concentration of the catalyst, various catalyst amounts were taken (Table 2,
Table 2. Effect of amount of LaCrO3 catalyst on oxidation of 1-phenyl ethanola
Entry
LaCrO3 (mol%)
Yieldb (%)
1
2c
3
4
5
6
7
10
10
—
5
97
—
—
81
97
97
98
10
15
20
aReaction conditions: 1-phenyl ethanol ¼ 1 mmol, 70% TBHP ¼ 0.129 g (1 mmol
equivalent of TBHP), time ¼ 0.5 h, temperature ¼ 90 ꢀC.
bYield determined by GC and GCMS analysis.
cWithout TBHP.

302
S. J. SINGH AND R. V. JAYARAM
a
Table 3. Liquid phase catalytic oxidation of various alcohols with 70% TBHP over LaCrO3
Entry
Alcohol
Time (h)
Product
Yieldb (%)
1
0.50
91
2
0.50
93
3
4
0.85
0.75
93
90
5
1.00
85
6
7
1.75
2.50
76
79
8
9
2.50
2.50
77
81
10
2.50
80
11
12
2.50
2.50
82
83
13
14
2.90
3.00
78
69
15
1.50
80
aReaction conditions: alcohol ¼ 10 mmol, 70% TBHP ¼ 1.29 g (10 mmol equivalent of TBHP),
LaCrO3 ¼ 1 mmol, temperature ¼ 90 ꢀC.
bIsolated yields.

OXIDATION OF ALCOHOLS OVER PEROVSKITES
303
entries 4–7). The optimum result was obtained when 10 mol% of catalyst was used.
Further increase in the weight of the catalyst did not have considerable effect on the
reaction.
To evaluate the scope of the LaCrO3=TBHP catalytic system, the oxidation of
various structurally and electronically diverse primary and secondary alcohols was
performed under solvent-free conditions (Table 3, entries 1–15). The oxidation of
1-phenyl ethanol provided 91% isolated yield of acetophenone within 30 min
(Table 3, entry 1). Other benzylic secondary alcohols reacted quantitatively, provid-
ing excellent yields of the products in short reaction times (Table 3, entries 2 and 3).
Such a short reaction time for completion was not observed in other reported cata-
lytic methods. Oxidation of benzoins is the best method for the synthesis of benzils,
as benzoins are easy to prepare. The present protocol provides a good catalytic sys-
tem for the oxidation of benzoin without the cleavage of carbon–carbon bonds,
which is a common undesirable feature associated with many other conventional oxi-
dation protocols (Table 3, entry 3). Aliphatic secondary alcohols with different levels
of hindrance reacted smoothly under the present conditions (Table 3, entries 4–6).
Oxidation of benzylic alcohols possessing a variety of electron-donating and
electron-withdrawing groups such as NO2, Cl, OMe, and CH3 were also studied,
and selective formation of aldehydes was obtained in good yields and tolerating
diverse electronic effects (Table 3, entries 7–12). The presence of substituents at
the ortho or para positions of the benzyl alcohol did not have much effect on the
reaction (Table 3, entries 9 and 10). Cinnamyl alcohol also reacted selectively with
carbon–carbon double bonds intact (Table 3, entry 13). Other primary alcohols such
as 2-phenyl ethanol (Table 3, entry 14) and nerol (Table 3, entry 15) were also oxi-
dized to provide 1-phenyl acetaldehyde and citral respectively in moderate to good
yields. Thus, the catalyst system proved to be highly active and selective for oxi-
dation of a wide range of alcohols.
A further set of experiments was carried out to examine the reusability of the
LaCrO3 catalyst for the oxidation of 1-phenyl ethanol. The catalyst was separated
after each run by filtration. After separation, the catalyst was washed with acetone
followed by diethyl ether and heated at 150 ꢀC for 2 h before use in the next cycle.
The catalyst reusability was tested for oxidation of 1-phenyl ethanol. The catalyst
was found to be reusable for up to six consecutive cycles with no significant loss
in activity. Further, to confirm the heterogeneous nature of the catalyst, an experi-
ment was conducted in which after 10 min the catalyst was filtered and the reaction
was continued with the filtrate. It was observed that the reaction did not proceed at
all, thereby establishing the truly heterogeneous nature of the catalyst. This is a
further advantage of the robust catalyst LaCrO3 as compared to the conventional
supported heterogeneous catalysts where leaching of the metal ions is a severe
problem.
To investigate the mechanistic pathway for the oxidation of alcohols over the
LaCrO3=TBHP catalytic system, a few experiments were carried out. The oxidation
of alcohols by this catalytic protocol possibly can be mediated by free-radical species
as evidenced by inhibition of the oxidation of 1-phenyl ethanol upon addition of rad-
ical scavengers such as 2,6-bis(1,1-dimethylethyl)-4-methyl phenol (Table 4, entry 2).
Thus, the function of LaCrO3 catalyst is probably to generate free radicals from
TBHP.

304
S. J. SINGH AND R. V. JAYARAM
Table 4. Influence of radical scavenger on the oxidation of 1-phenyl ethanola
Entry
1
Alcohol
Time (h)
Product
Yieldb (%)
0.50
97
2c
0.50
0
aReaction conditions: alcohol ¼ 1 mmol, 70% TBHP ¼ 0.129 g (1 mmol equivalent of TBHP),
LaCrO3 ¼ 0.1 mmol, temperature ¼ 90 ꢀC.
bYields determined by GC and GCMS analysis.
cIn presence of 1 mmol radical scavenger.
CONCLUSION
In conclusion, LaCrO3 was found to be an efficient catalyst for selective oxi-
dation of alcohols to carbonyl compounds in the presence of TBHP as an oxidant
under mild reaction conditions. The ease of preparation of this catalyst, high chemi-
cal and thermal stability, and greater substrate compatibility makes it an attractive
and useful alternative to the present range of catalysts for the oxidation of alcohols.
Other advantages offered by this protocol include good yield of aldehydes and
ketones in a short time, high selectivity for the oxidation at the alcoholic group,
catalyst reusability, and the use of solvent-free condition.
EXPERIMENTAL
Preparation of Perovskite Catalysts
=
LaMO3 (M Cr, Co, Fe, Mn, Ni) perovskites were prepared by the method
described by Kremenic et al.[12] The corresponding metal nitrates and citric acid were
dissolved in distilled water in the desired proportions. The solution was evaporated
in a rotary evaporator until it became a viscous syrup. The precursors so obtained
were heated in a vacuum oven at 100 ꢀC for 5 h and were then heated for 4 h at
1023 K, 973 K, 973 K, 1023 K, and 923 K for LaCrO3, LaMnO3, LaCoO3, LaNiO3,
and LaFeO3 respectively to obtain a single perovskite phase as confirmed by X-ray
diffraction (XRD).[11]
Oxidation of Alcohols
To a clean, dry, 25-mL, round-bottomed flask containing 10 mmol of alcohol
was added 1.29 g of 70% TBHP (10 mmol equivalent of TBHP) followed by 1 mmol
of LaMO3. The mixture was stirred at 90 ꢀC. The progress of the reaction was mon-
itored by thin-layer chromatography (TLC) and gas chromatography. After an
appropriate time, the catalyst was separated by filtration. The pure products were

OXIDATION OF ALCOHOLS OVER PEROVSKITES
305
obtained after column chromatography on silica gel using an appropriate
combination of petroleum ether=ethyl acetate as eluent.[13]
Spectral Data of Selected Products
1
Table 3 Entry 3. H NMR (300 MHz, CDCl3, 25 ꢀC), d ppm: 7.50 (t, 4 H,
J ¼ 7.5 Hz), 7.65 (t, 2 H, J ¼ 7.5 Hz), 7.97 (d, 2 H, J ¼ 7.5 Hz). Anal. calcd. for
C14H10O2: C, 79.91; H, 4.75. Found: C, 79.94; H, 4.69. MS (EI, 70 eV): 210 (5)
(Mþ), 181 (2), 152 (2), 105 (100), 77 (48), 51 (17).
1
Table 3, Entry 4. H NMR (300 MHz, CDCl3, 25 ꢀC), d ppm: 0.84 (s, 3H),
0.91 (s, 3H), 0.96 (s, 3H), 1.38 (m, 2H), 1.69 (ddd, 2H, J ¼ 4, 9, 13 Hz), 1.84 (d,
1H, J ¼ 18 Hz), 1.94 (m, 1H), 2.35 (dt, 1H, J ¼ 4, 18 Hz). Anal. calcd. for
C10H16O: C, 78.80; H, 10.50. Found: C, 78.71; H, 10.37. MS (EI, 70 eV): 152 (32)
(Mþ), 137 (6), 123 (4), 109 (28), 95 (100), 81 (75), 67 (25), 41 (46).
1
Table 3, Entry 5. H NMR (300 MHz, CDCl3, 25 ꢀC), d ppm: 0.85 (d, 3H,
J ¼ 6.6 Hz), 0.84 (d, 3H, J ¼ 6.8 Hz), 1.33 (d, 3H, J ¼ 10.0 Hz), 1.25–2.30 (m, 9H).
Anal. calcd. for C10H18O: C, 77.80; H, 11.67. Found: C, 77.11; H, 11.36. MS (EI,
70 eV): 154 (32) (Mþ), 139 (42), 112 (100), 111 (28), 97 (29), 70 (34), 69 (77), 55
(53), 41 (64), 40 (5).
1
Table 3, Entry 9. H NMR (300 MHz, CDCl3, 25 ꢀC), d ppm: 7.52 (d, 2H,
J ¼ 8.4 Hz), 7.82 (d, 2H, J ¼ 8.4 Hz), 9.98 (s, 1H). Anal. calcd. for C7H5OCl: C,
59.75; H, 3.55. Found: C, 59.10; H, 3.41. MS (EI, 70 eV): 142 (24), 141 (12), 140
(73) (Mþ), 139 (100), 113 (20), 111 (61), 77 (19), 76 (10), 75 (33), 74 (19), 51 (19),
50 (29).
1
Table 3, Entry 10. H NMR (300 MHz, CDCl3, 25 ꢀC), d ppm: 7.27–7.56 (m,
3H), 7.90–7.94 (dd, 1H, J ¼ 1.8, 5.9), 10.48 (d, 1H). Anal. calcd. for C7H5OCl: C,
59.75; H, 3.55. Found: C, 59.53; H, 3.28. MS (EI, 70 eV): 142 (25), 141 (13), 140
(76) (Mþ), 139 (100), 113 (15), 111(46), 77 (22), 76 (23), 75 (29), 74 (18), 51 (19),
50 (30).
1
Table 3, Entry 12. H NMR (300 MHz, CDCl3, 25 ꢀC), d ppm: 2.43 (s, 3H),
7.32 (d, 2H, J ¼ 8.1 Hz), 7.77 (d, 2H, J ¼ 8.4 Hz), 9.95 (s, 1H). Anal. calcd. for
C8H8O: C, 79.90; H, 6.66. Found: C, 79.39; H, 6.29. MS (EI, 70 eV): 120 (91)
(Mþ), 119 (96), 91 (100), 65 (30), 51 (11), 50 (7), 41 (4).
1
Table 3, Entry 13. H NMR (300 MHz, CDCl3, 25 ꢀC), d ppm: 6.68–6.76 (m,
1H), 7.40–7.58 (m, 6H), 9.70 (d, 1H). Anal. calcd. for C9H8O: C, 81.71; H, 6.05.
Found: C, 81.12; H, 5.92. MS (EI, 70 eV): 132 (64) (Mþ), 131 (100), 103 (55), 77
(42), 63 (8), 51 (35), 40 (2).
1
Table 3, Entry 15. H NMR (300 MHz, CDCl3, 25 ꢀC), d ppm: 1.61 (s, 3H),
1.68 (s, 6H), 2.12–2.27 (m, 4H), 5.06 (m, 1H), 5.88 (d, 1H, J ¼ 8.0 Hz), 9.99 (d, 1H,
J ¼ 8.0 Hz). Anal. calcd. for C10H16O: C, 78.84; H, 10.51. Found: C, 78.29; H, 9.95.
MS (EI, 70 eV): 152 (17) (Mþ), 137 (23), 123 (8), 110 (63), 95 (30), 82 (74), 69 (88), 54
(17), 41 (100), 40 (6).

306
S. J. SINGH AND R. V. JAYARAM
ACKNOWLEDGMENT
S. J. S. thanks the Council of Scientific and Industrial Research, New Delhi,
India, for the award of a senior research fellowship.
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