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D. Talukdar et al.
LETTER
a
b
(2) (a) Mannan, S.; Sekar, G. Tetrahedron Lett. 2008, 49, 1083.
Table 5 Yield of Products (Acids) Without and After Regeneration
of the Catalyst
(b) Hainess, A. H. Method of Oxidation of Organic
Compounds; Academic: New York, 1988. (c) Ogliaruso, M.
A.; Wolfe, J. F. Synthesis of Carboxylic Acids, Esters, and
their Derivatives, In The Chemistry of Functional Groups;
Patai, S.; Rappoport, Z., Eds.; Wiley: Chichester, 1991.
(3) (a) Heilbron, I.; Jones, E. R. H.; Sondheimer, F. J. Chem.
Soc. 1949, 604. (b) Bowers, A.; Halsall, T. G.; Jones, E. R.
H.; Lemin, A. J. J. Chem. Soc. 1953, 2548.
Run
Time
h)
Yield without
regeneration (%) regeneration (%)
Yield after
(
1st (fresh)
2nd
6
97
94
92
89
87
87
–
6.5
6.5
7
94
93
93
92
90
(
4) (a) Abiko, A.; Roberts, J. C.; Takemasa, T.; Masamone, S.
Tetrahedron Lett. 1986, 27, 4537. (b) Sebelmeir, J.; Ley, S.
V.; Baxendale, I. R.; Baumann, M. Org. Lett. 2010, 12,
3rd
4th
3
618.
(5) (a) Barker, I. R. L.; Dahm, R. H. J. Chem. Soc. B 1970, 650.
b) Mamdouh, A. N.; Pujol, M. D. Tetrahedron Lett. 1990,
1, 2273.
5th
7
(
3
6th
7.5
a
(6) Rangaswamy, M.; Lakshminarasimhan, S.; Ramadas, C. V.
Isolated yield of product.
b
Proc. Indian Acad. Sci. 1970, 72, 292.
Carried out with 4-nitrobenzaldehyde (1 mmol) at r.t. in MeCN and
H O (3 mmol) as the oxidant using 5 wt% of the TSV.
(
7) Corey, E. J.; Gilmann, N. W.; Ganem, B. E. J. Am. Chem.
Soc. 1968, 90, 5616.
2
2
(
(
8) Mannam, S.; Sekar, G. Tetrahedron Lett. 2008, 49, 1083.
9) Chakraborty, D.; Gowda, R. R.; Malik, P. Tetrahedron Lett.
2009, 50, 6553.
Typical Oxidation Procedure
VO(acac) (0.007 g 4 mol%) was dissolved in 30% H O (0.34 mL,
2
2
2
(10) Malik, P.; Chakraborty, D. Tetrahedron Lett. 2010, 51,
521.
11) Sodhi, R. K.; Paul, S.; Clark, J. H. Green Chem. 2012, 14,
649.
12) Späth, E.; Pailer, M.; Schmid, M. Chem. Ber. 1941, 74,
1552.
13) Sato, K.; Hyodo, M.; Takagi, J.; Aoki, M. J.; Noyori, R.
Tetrahedron Lett. 2000, 41, 1439.
14) (a) Yamaguchi, K.; Mori, K.; Mizugaki, T.; Ebitani, K.;
Kaneda, K. J. Org. Chem. 2000, 65, 6897. (b) Kamata, K.;
Ishimoto, R.; Hirano, T.; Kuzuya, S.; Uehara, K.; Mizuno,
N. Inorg. Chem. 2010, 49, 2471.
3
mmol); the color of the mixture changed to reddish brown. To this
3
mixture, 4-chlorobenzaldehyde (0.14 g, 1 mmol) dissolved in the
minimum amount of MeCN was added and the mixture stirred.
Progress of the reaction was monitored by TLC. On completion of
(
(
(
(
1
the reaction, MeCN was removed under reduced pressure and H O
2
was added (3 mL). The product was extracted with EtOAc (3 × 10
mL), and the organic layer was dried over anhyd Na SO . Finally,
2
4
the product was purified by column chromatographic technique.
Typical Procedure for the Preparation of TiO /VO(acac) Cat-
2
2
alyst
2
2
TiO /VO(acac) was prepared by the reported procedure.
2
2
(
15) (a) Hussain, S.; Talukdar, D.; Bharadwaj, S. K.; Chaudhuri,
M. K. Tetrahedron Lett. 2012, 53, 6512. (b) Silva, J. A. L.;
Silva, J. J. R. F.; Pombeiro, A. J. L. Coord. Chem. Rev. 2011,
Typical Oxidation Procedure with TiO /VO(acac)
2
2
TiO /VO(acac) (0.0075 g, 5 wt%) was taken in 30% H O (0.34
2
2
2
2
mL, 3 mmol). To this mixture, 4-nitrobenzaldehyde (0.15 g, 1
mmol) dissolved in the minimum amount of MeCN was added, and
the mixture was stirred. Progress of the reaction was monitored by
TLC. On completion of the reaction, the mixture was filtered to re-
cover the catalyst, and MeCN was removed under reduced pressure.
The product was extracted with EtOAc (3 × 10 mL) and dried over
anhyd Na SO . The recovered catalyst was washed with cold EtOH
2
55, 2232.
(
16) (a) Velusamy, S.; Punniyamurthy, T. Eur. J. Org. Chem.
2
003, 3913. (b) Bogdał, D.; Łukasiewicz, M. Synlett 2000,
1
43.
(
(
(
17) Kirumakki, S.; Samarjeewa, S.; Harwell, R.; Mukherjee, A.;
Herber, R. H.; Clearfield, A. Chem. Commun. 2008, 5556.
18) Mizuno, N.; Kamata, K. Coord. Chem. Rev. 2011, 255,
2
4
and dried at 120 °C for 1 h and then used for further reaction. Final-
ly, the product was purified by column chromatographic technique.
2
358.
19) (a) Kobayashi, H.; Yamanaka, I. J. Mol. Catal. A: Chem.
008, 294, 37. (b) Li, Z.; Liu, L.; Hu, J.; Wu, S.; Huo, Q.;
Guan, J.; Kan, Q. Appl. Organomet. Chem. 2012, 26, 252.
c) Raghavan, S.; Rajendra, A.; Joseph, S. C.; Rasheed, M.
A. Synth. Commun. 2001, 31, 1477.
2
Acknowledgment
(
D.T. wishes to thank the Council of Scientific and Industrial Re-
search (CSIR), New Delhi, India for financial support. K.S. thanks
Tezpur University for the experimental facilities provided to him
during his work. The authors wish to thank Prof. M. K. Chaudhuri,
VC, Tezpur University for his encouragement and valuable sugge-
stion during this work.
(20) (a) Gopinath, R.; Barkataky, B.; Talukdar, B.; Patel, B. K. J.
Org. Chem. 2003, 68, 2944. (b) Gopinath, R.; Patel, B. K.
Org. Lett. 2000, 2, 577.
(21) Ligtenbarg, A. G. J.; Hage, R.; Feriga, B. L. Coord. Chem.
Rev. 2003, 237, 89.
(
22) Kantam, M. L.; Neelima, B.; Reddy, C. V.; Chaudhuri, M.
K.; Dehury, S. K. Catal. Lett. 2004, 95, 19.
23) Regeneration of the Catalyst
Reference and Notes
(
To a solution of VO(acac) (265 mg) in anhyd THF (50 mL),
2
(
1) Present address: Department of Chemistry, Dibrugarh
the recovered catalyst (1 g) was added, and the mixture was
stirred at r.t. under nitrogen atmosphere. The solid catalyst
was filtered and dried under vacuum.
University, Dibrugarh 786004, Assam, India.
Synlett 2013, 24, 963–966
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