Silica supported Thallium (III) Nitrate: An effective oxidant for oxidation of alcohols to the carbonyl compounds

Article abstract of DOI:10.4067/S0717-97072015000300005

Thallium (III) Nitrate Supported on Silica gel was found to be an efficient reagent system for oxidation of primary and secondary alcohols to their corresponding carbonyl compounds under mild conditions. The striking features of our method are: short reaction times, formation of no over oxidation products due to high selectivity and mild nature of oxidant, easy work-up procedure, high yields and carbon carbon double or triple bond functional group in the alcohol structure does not oxidize to other group.

Full text of DOI:10.4067/S0717-97072015000300005

J. Chil. Chem. Soc., 60, Nº 3 (2015)
SILICA SUPPORTED THALLIUM (III) NITRATE: AN EFFECTIVE OXIDANT FOR OXIDATION
OF ALCOHOLS TO THE CARBONYL COMPOUNDS
ABBAS AMINI MANESH* AND TAHEREH NAZARI
Department of Chemistry, Payame Noor University, 19395-4697 Tehran, I. R. of IRAN.
ABSTRACT
*
Thallium (III) Nitrate Supported on Silica gel was found to be an efficient reagent system for oxidation of primary and secondary alcohols to their corresponding
carbonyl compounds under mild conditions. The striking features of our method are: short reaction times, formation of no over oxidation products due to high
selectivity and mild nature of oxidant, easy work-up procedure, high yields and carbon carbon double or triple bond functional group in the alcohol structure does
not oxidize to other group.
Key words: Oxidation, Thallium (III) Nitrate, Alcohols, Silica gel.
INTRODUCTION
The oxidation reactions were performed under mild and completely
heterogeneous conditions with good yields, (Table 1).
The oxidation of alcohols to the corresponding carbonyl compounds is
one of the most fundamental and important transformations in synthetic
organic chemistry. In particular, selective cascade oxidative transformations
of alcohols to carbonyl compounds (i.e., primary alcohols → aldehydes →
carboxylic acids; secondary alcohols → ketones → esters; cycloalkanols →
cycloalkanones → lactones or cyclic α, β- enones, etc.) are attractive, since
the target molecule can be obtained directly in one-pot sequences. To date,
many excellent catalytic methods have been developed for alcohol oxidations
RESULTS AND DISCUSSION
The XRD profiles of the samples at 298 °K are shown in Figure 1 and 2.
Powder X-ray diffraction (XRD) patterns were recorded on a Philips PW-1840
X-ray diffractometer (XRD) with Cu Kα radiation. The intensity data were
collected over a 2θ range of 10−90°. Comparison of the 2 XRD spectra showed
that Tl(NO ) particles were supported on silica gel ( any increase in width of
3
3
1-6
18-19
.
The concept of using reagent adsorbed on inert inorganic supported has
crystal sheets of materials cause decrease in peak width of XRD spectra) .
The XRD results revealed the presence of Tl(NO ) over the amorphous
been applied in organic synthesis. There is current research and general
interest in heterogeneous systems because of the importance such systems
3
3
SiO2 matrix in the case of Tl(NO ) -SiO (see 2θ = 10–60°), and some
3
3
2
7
have in industry and in developing technologies . Such efficiency resulting
overlapped regions. The particles sizes of the Tl(NO ) on SiO according to
3 3 2
from inorganic material- supported reagent may come from the combination of
three factors: (i) an increase in the effective surface area for reaction; (ii) the
presence of pores which constrain both substrate and catalyst and thus lowers
the activation entropy of reaction;(iii) the acceleration of the reaction resulting
scherrer equation was estimated as 90 nm (figure 2).
8
from bringing substrate and reagent into proximity . These novel reagents have
advantages over the conventional homogeneous solution techniques, such as:
easy set- up and work-up, mild experimental condition, and high yield and
9-10
selectivity .
During the course of our systematic study on oxidation of organic
11-17
compounds ,
we report herein an oxidation of alcohols to the carbonyl
compounds with Thallium (Ш) Nitrate (TTN) supported on Silica gel catalyzed
by AlCl in solution, scheme 1.
3
Figure 1: XRD spectrum of SiO2
Scheme 1
Since transition metal cations are highly toxic and carcinogenic species, its
application with any dispersion is very interesting for organic and biochemists.
In this article, a new procedure with clean work-up and easy removal of
chemical waste (due to the heterogeneous nature) was described. Different
types of alcohols (primary and Secondary) were subjected to the oxidation by
thallium (III) nitrate supported on Silica gel (TTN/Silica gel) in the presence of
Figure 2: XRD spectrum of TTN supported on SiO2
AlCl . The overall reaction is best formulated in the scheme 2.
3
The results of the conversions of various alcohols to their corresponding
carbonyl compounds are presented in Table 1.
Scheme 2
e-mail: a_aminima@yahoo.com
3001

J. Chil. Chem. Soc., 60, Nº 3 (2015)
Table 1: Oxidation of primary and secondary alcohols using TTN/SiO in the presence of AlCl
2
3
a,b,c
Entry
Substrate
OH
Product
Time(min)
35
Yield (%)
O
H
1
75
OH
O
2
25
56
OH
O
3
4
5
60
35
90
67
80
63
O
OH
OH
O
OH
O
6
7
45
67
78
OH
CH3
O
25
CH3
OH
O
8
9
45
73
60
60
90
60
65
43
53
73
OH
O
1
0
CH (CH ) CH OH
CH
CH COCH
CH (CH
3
(CH
2
)
6
CHO
CH CH
CHO
3
2 6
2
11
CH
3
CHOHCH
(CH
2
CH
2
CH
3
3
2
2
3
1
2
CH
3
2
)
2
CH
2
OH
3
)
2 2
a
20-24
Products were characterized by their physical costants, comparison with authentic samples and melting points of 2,4-dinitro phenyl hydrazone derivatives
b
c
and IR and NMR spectra; Isolated yields ; Reaction Condition: alcohol (1 mmol), DMSO, CH CN, TTN/Silica gel(1 mmol), AlCl under reflux.
3
3
As shown in Table 1, not only sterically demanding secondary alcohols
(entries 3, 6, 7), but also unsaturated alcohols (entries 2, 4, 5, 9) were oxidized
to the corresponding α, β-unsatureted carbonyl compounds without the
cleavage of carbon-carbon double bond, scheme 3.
It is difficult to oxidize primary alcohols selectively to the corresponding
aldehydes, but in this method, we oxidized primary alcohols to the aldehydes
and no acid was formed due to over oxidation of the regenerated aldehydes
(entries 1, 2, 4, 5, 9, 10 and 12), scheme 4.
7
5%
0%
Scheme 4: Selective oxidation of benzyl alcohol
In order to establish the catalytic activity of our oxidant (TTN/Silica gel),
we compared our results on the oxidation of diphenyl methanol (as a typical
example) with data from the literature (Table 2). As shown in Table 2, the
previously reported procedures suffer from one or more disadvantages such as
elevated reaction temperatures, longer reaction times, and special efforts for
the preparation of catalyst.
Scheme 3: Selective oxidation of unsaturated alcohol
3
002

J. Chil. Chem. Soc., 60, Nº 3 (2015)
Table 2: Comparison of the different methods used for the oxidation of diphenyl methanol
a
Entry
Reagent
Time (min)
Yield (%)
Reference
1
2
3
aqueous solution of TBAOX catalyzed by CuPc
30
80
98
99
25
26
27
Oxone (2.4 equiv.), AlCl (2.7 equiv.)
240
480
3
V O (0.05 mmol) aq TBHP (70%, 4 mmol)
2
5
[
Co(L) ](NO ) .2CH OH(0.05 mmol),
2
3
3
3
4
5
480
3300
60
36
94
67
28
H O (3 mmol)
2
2
silica based cobalt (II) interphase
5
catalyst (0.25% mol), NHPI (1 mmol), O2
TTN/Silica gel (0.834 g, 1 mmol TTN),
6
This method
AlCl (0.75 mmol)
3
a
Isolated Yield.
This procedure offers several major advantages: (1) the use of a
commercially available, cheap, and chemically stable reagent and oxidant; (2)
highly efficient for the selective oxidation of structurally diverse alcohols in
good yields; (3) control over the degree of oxidation offers access to aldehydes
carbon carbon double or triple bond functional group in the alcohol structure
does not oxidize to other functional group.
EXPERIMENTAL
General Remarks
(and not to acids); (4) excellent chemoselectivity. We believe the present
method to be an improvement with respect to other procedures.
Chemicals such as alcohols, Thallium (III) nitrate, AlCl , DMSO,
3
acetonitrile and silica gel were purchased from Fluka, Merck and Aldrich
chemical companies. The oxidation products were characterized by comparison
1
of their Spectra (IR, H NMR), TLC and physical data with the authentic
samples.
Preparation of the TTN/Silica gel reagent
Thallium nitrate (TTN.3H O) (20 g, 45 mmol) was dissolved in acetone
2
(60 mL) and Silica gel (20 g) was then added under stirring at 25 ºC for 45
min. The excess solvent was evaporated under reduced pressure using a rotary
evaporator. The white powder solid was dried in vacuum desiccators. TTN/
Silica gel can be stored for at least 2 months in air and at room temperature
without losing its activity. (1 g TTN/Silica gel contains 0.468 g TTN or 1.19
mmol TTN).
General procedure for oxidation of alcohols in solution
In a round-bottomed flask (25 mL) equipped with a magnetic stirrer and
condenser, a solution of alcohols (1 mmol) and DMSO (0.2 mol %) in CH CN
3
(5 mL) was prepared. TTN/Silica gel (0.834 g which contain 1 mmol TTN) and
AlCl (0.75 mmol) was added to the solution and the mixture was refluxed for
3
the appropriate times as indicated in Table 1.
The progress of the reaction was followed by TLC (CCl /EtOAC: 4/1).
4
After completion, the reaction mixture was filtrate and the solid material was
washed with CH CN (10 mL). The filtrate was evaporated and the resulting
3
crude material was purified by column chromatography on silica gel to afford
the pure product.
Products were characterized by their physical constants, comparison with
2
0-24
authentic samples and IR and NMR spectra.
ACKNOWLEDGEMENTS
The authors acknowledge to Hamedan Payame Noor University Research
Councils for support of this work.
REFERENCES
1
2
.
.
B.M. Trost, I. Fleming, S.V. Ley, Comprehensive Organic Synthesis:
Oxidation, Pergamon Pr, (1991).
G. Tojo, M. Fernandez, Oxidation of Alcohols to Aldehydes and Ketones;
Springer; Berlin, (2006).
C. Y. Lorber, J. A. Osborn, Tetrahedron Lett., 37, 853 (1996).
H. Hosseini-Monfared, C. Nather, H. Winkler, C. Janiak, Inorganica
Chimica Acta 391, 75, (2012).
F. Rajabi, B. Karimi, J. Mol. Catal. A: Chem. 232, 95 (2005).
R. A. Sheldon, I. W. C. E. Arends, A. Dijkman, Catal. Today, 57, 157
Scheme 5 shows the proposed mechanism for this oxidation.
CONCLUSION
3
4
.
.
In this article we would like to report a simple and convenient method
for the effective conversion of alcohols to their corresponding aldehydes or
ketones under heterogeneous conditions. The striking features of our method
are: short reaction times, formation of no over oxidation products due to high
selectivity and mild nature of oxidant, easy work-up procedure, high yields and
5
6
.
.
(2000).
3
003

J. Chil. Chem. Soc., 60, Nº 3 (2015)
7
8
.
.
.
E. D. Taylor, C. S. Chiang, A. McKillop, J. F. White, J. Am. Chem. Soc.,
8(21), 6750 (1976).
K. Burgess, Solid- Phase Organic Synthesis, 1 th ed.; Wiley- Interscience,
1999).
N. Noroozi-Pesyan, A. H. Dabbagh, Molecules, 10, 1364 (2005).
19. D. A. Skoog, D. M. West, Principles of Instrumental Analysis, Holt-
Saunders, Tokyo, (1987).
20. Vogel’s Textbook of practical organic chemistry, fourth edition, (1986).
21. G. Sarifuddin, A. Rajakumar, RSC. Adv. 2, 7781 (2012).
22. S. K. M. Islam, S. Paul, A. S. Roy, P. Mondal, J. Inorg. Organomet.
Polym., 23(3), 560 (2013).
9
(
9
1
1
0. A. Mckillop, D.W. Young, Synthesis, 481 (1979).
1. A. Khazaei, A. Amini Manesh and A. Rostami, J. Chem. Res., 6, 391
23. C. J. Pouchert, The Alderich Library of Infrared Spectra, Edition 3,
Alderich Chemical Company, Inc. (1981).
(2005).
1
1
1
2. A. Khazaei, A. Amini Manesh, J. Braz. Chem. Soc., 16 (4), 874 (2005).
3. A. Khazaei, A. Amini Manesh, A. Rostami, J. Chem. Res., 10, 695 (2004).
4. A. Khazaei, A. Amini Manesh, A. Rostami, Phosphorus, Sulfur Silicon
Relat. Elem., 179 (12), 2483 (2004).
24. C. J. Pouchert, The Alderich Library of NMR Spectra, Edition 2, Alderich
Chemical Company, Inc. Vol. 1, (1983).
25. A. Rezaeifard, M. Jafarpour, A. Naeimi, M. Salimi, Inorg. Chem.
Commun., 15, 230 (2012).
1
1
1
1
5. A. Khazaei, A. Amini Manesh, Synthesis- Stuttgart, 12, 1929 (2005).
6. A. Khazaei, A. Amini Manesh, J. Chin. Chem. Soc., 52 (5), 1017 (2005).
7. A. Khazaei, A. A. Manesh, Mendeleev Commun., 16 (2), 109 (2006).
8. H. Freiser, Concepts and Calculations in Analytical Chemistry, CRC,
Florida, (1992).
26. S. Wu, H. Ma, Z. Lei, Tetrahedron, 66, 8641 (2010).
27- K. Alagiri, K. Ramaiah Prabhu, Tetrahedron, 67, 8544 (2011).
28- A. Nemati Kharat, A. Bakhoda, B. Tamaddoni Jahromi, Polyhedron, 30,
2768 (2011).
3
004