OXIDATION OF DITHIOLS
99
TABLE 5
REFERENCES
The oxidation of dithiols by KMnO4 with different
temperature and solvent in the presence of H5PMo10V2O40
1. Varma, R.S. Green Chem. 1999, 1, 43.
2
. Li, C.-J.; Chen, L. Chem. Soc. Rev. 2006, 5, 68.
. Pryor, W.A.; Church, D.F.; Govindan, C.K.; Crank, G. J. Org. Chem. 1982,
7, 156.
4. Briand, L.E.; Baronelti, G.T.; Thomas, H.J. Appl. Catal. A: Gen. 2003, 256,
7.
3
4
Time
(h)
Temperature
Yield
(%)
◦
Entry
solvent
( C)
3
5
6
7
8
. Kesavan, V.; Bonnet-Delpon, D.; Begue, J. P. Synthesis 2000, 223.
. Kozhevnikov, I.V. Chem. Rev. 1998, 98, 171.
. Schwegler, M.A.; van Bekkum, H.; Munck, N. Appl. Catal. 1991, 74, 191.
. Kozhevnikov, I.V.; Matveev, K.I. Appl. Catal. 1983, 5, 135.
1
2
3
4
7
8
9
EtOH + H2O
EtOH + H2O
EtOH + H2O
EtOH + H2O
H2O
H2O
H2O
H2O
MeOH + H2O
MeOH + H2O
MeOH + H2O
MeOH + H2O
8
8
8
10
8
8
10
12
10
12
17
18
80
60
45
25
90
70
50
25
90
60
45
25
95
92
83
73
80
70
62
34
86
67
65
35
9. Kozhevnikov, I.V. Catal. Rev.-Sci. Eng. 1995, 37(2), 311.
0. Izumi, Y.; Hasebe, R.; Urabe, K. J. Catal. 1983, 84, 402.
1. Soeda, H.; Okuhara, T.; Misono, M. Chem. Lett. 1994, 909.
2. Hill, C.L. (Guest Ed.). Chem. Rev. 1998, 98, 1.
3. Keggin, J.F. Nature 1933, 131, 908.
1
1
1
1
1
10
13
14
15
16
4. Misono, M. Catal. Rev. Sci. Eng. 1987, 29, 269.
15. Kozhevnikov, I.V. Catal. Rev. Sci. Eng. 1995, 37, 311.
1
1
1
6. Okuhara, T.; Mizuno, N.; Misono, M. Adv. Catal. 1996, 41, 113.
7. Song, I.K.; Barteau, M.A. J. Mol. Catal. 2004, 212, 229.
8. Imamura, K.; Tano, K.; Kobeppn, S. Jpn. Kokai Tokkyo Koho, JP Patent
1
087811, 1998.
1
2
2
9. Misono, M. Catal. Rev. Sci. Eng. 1987, 29, 269;
0. Misono, M. Catal. Rev. Sci. Eng. 1988, 30, 339.
1. Izumi, Y.; Urabe, K.; Onaka, M. Zeolite,Clay and Heteropoly Acid in Or-
ganic Reactions; Kodansha/VCH: Tokyo, 1992, p. 99.
2. (a) Kapustin, G.I.; Brueva, T.R.; Klyachko, A.L.; Timofeeva, M.N.; Ku-
as the reaction temperature was raised. As expected, under all
conditions, H5[PMo10V2O40] showed the highest yields for all
substrates. Some controlled experiments, at different tempera-
ture, showed that the yields of disulfide are also a function of
time: the longer the time, the higher the yield.
2
likov, S.M; Kozhevnikov, I.V. Kinet. Katal. 1990, 31, 1017;
23. (b) Misono, M.; Okuhara, T. Chemtechnology 1993, 23, 23.
2
2
2
4. (a) Tatematsu, S.; Hibi, T.; Okuhara, T.; Misono, M. Chem. Lett. 1984,
65;
5. (b) Okuhara, T.; Nishimura, T.; Misono, M. Stud. Surf. Sci. Catal. 1996,
01, 581.
6. Ono, I.; Koyano, G.; Misono, M. 82nd National Conference on Catalysis,
Matsuyama, 1998.
8
4
.
CONCLUSION
The H5[PMo10V2O40] heteropolyacid was the most success-
1
ful heteropolyacids in this reaction. Although it is difficult to
offer an explanation for the different activity between these
HPAs, certainly there is a complex relationship between the ac-
tivity and structure of polyanion. By changing the constituent
elements of polyanion (both hetero and addenda atoms), the acid
2
2
7. Toyoshi, Y.; Nakato, T.; Okuhara, T. Bull. Chem. Soc. Jpn. 1998, 71, 2817.
8. Liu, J.; Liu, S.; Qu, L.; Pope, M.T.; Rong, C. Transition Met. Chem. 1992,
1
7, 311.
29. Liu, J.-F.; Cehn, Y.-G.; Meng, L.; Guo, J.; Liu, Y.; Pope, M.T. Polyhedron
strength of HPAs as well as its catalytic activity is able to vary
1
998, 17, 1541.
in a wide range.[ For the first time, by an inexpensive solid 30. Perrin, D.D.; Armarego, W.L.F. Purification of Laboratory Chemicals, 3rd
18]
Edition; Pergamon Press: New York, 1988.
acid catalyst and an easily prepared H5[PMo10V2O40] oxida-
3
3
3
3
1. Tsigdinos, G.A.; Hallada, C.J. Inorg. Chem. 1968, 7, 437.
2. Preyssler, C. Bull. Soc. Chim. Fr. 1970, 30.
tion of dithiols to the corresponding cyclic disulfides have been
studied. The results show that the catalyst type, the nature and
positions of substituents and temperature are important factors.
3. Cavani, F.; Comuzzi, C. J. Catal. 1996, 160, 317.
4. Shikata, S.; Nakata, S.; Okuhara, T.; Misono, M. J. Catal. 1997, 166, 263.
The keggin-type polyoxometalates lead to effective reaction in 35. Khodaei, M.M.; Mohammadpoor-Baltork, I.; Nikoofar, K. Bull. Korean
Chem. Soc. 2003, 24, 885.
comparison with Well-dawson type polyoxometalates.