SHORT PAPER
Regeneration of Carbonyl Compounds from Oximes and N,N-Dimethyl Hydrazones
1885
H3CO
CHO
OCH3
H3CO
CH=N-OH
OCH3
95%
+
H3CO
CHO
OCH3
H3CO
CH=N-NMe2
K5CoW12O40.3H2O
RT/CH3CN
OCH3
85%
+
H3CO
CH=N-NHPh
OCH3
H3CO
CH=N-NHPh
OCH3
OCH3
unchanged
or
OCH3
CH=N-NHCONH2
H3CO
CH=N-NHCONH2
H3CO
unchanged
Scheme 2
Oxime (Entry 6)
(10) Aizpurua, J. M.; Juaristi, M.; Lecea, B.; Palomo, C.
1H NMR (200 MHz, CDCl3): = 3.65 (s, 2 H), 3.78 (s, 2 H), 7.03–
7.35 (m, 3 H), 7.81 (m, 1 H).
Tetrahedron 1985, 41, 2903.
(11) Ranu, B. C.; Sarkar, D. C. J. Org. Chem. 1988, 53, 878.
(12) Olah, G. A.; Liao, Q.; Lee, C. S.; Surya Prakash, G. K.
Synlett 1993, 427.
(13) Barhate, N. B.; Gajare, A. S.; Wakharkar, R. D.; Sudalai, A.
Tetrahedron Lett. 1997, 38, 653.
(14) Joseph, R.; Sudalai, A.; Ravindranathan, T. Tetrahedron
Lett. 1994, 35, 5493.
(15) Demir, A. S.; Tanyeli, C.; Altinel, E. Tetrahedron Lett.
1997, 38, 7267.
(16) Bandgar, B. P.; Kunde, L. B.; Thote, J. L. Synth. Commun.
1997, 27, 1149.
(17) Varma, R. S.; Dahiya, R.; Saini, R. K. Tetrahedron Lett.
1997, 38, 8819.
(18) Bose, D. S.; Srinivas, P. Synlett 1998, 977.
(19) (a) Chaudhuri, S. S.; Akamanchi, K. G. Tetrahedron Lett.
1998, 39, 3209. (b) Bose, D. S.; Narsaiah, A. V. Synth.
Commun. 1999, 29, 937.
Potassium DodecatangestocobaltateTrihydrate (K5CoW12O40·3
H2O) Catalyst
Cobaltous acetate (5.0g, 0.01 mol) and sodium tangestate (39.6g,
0.06 mol) were initially treated with acetic acid (5 mL) and H2O at
pH 6.5 to 7.5 to give sodium tangestodicobalt(II)ate. The sodium
salt was then converted into the potassium salt by treatment with po-
tassium chloride (26.0 g). Finally, the cobalt(II) complex was oxi-
dized to the cobalt(III) complex by potassium persulfate (21.0 g) in
H2SO4 (2 M; 80 mL). The crystals of K5CoW12O40·3 H2O were
dried at 200 ºC. After recrystallization with MeOH, potassium
dodecatangestocobaltate trihydrate (K5CoW12O40.3 H2O) was ob-
tained.
Yield: 17.5g (55%); light blue solid.
(20) Mitra, A. K.; De, A.; Karchaundari, N. Synlett 1998, 1345.
(21) Bose, D. S.; Narsaiah, A. V. Synth. Commun. 2000, 30,
1153.
(22) Shirini, F.; Zolfigol, M. A.; Mallakpour, B.; Mallakpour, S.
E.; Hajipour, A. R.; Baltork, I. M. Tetrahedron Lett. 2002,
43, 1555.
(23) Varma, R. S.; Meshram, H. M. Tetrahedron Lett. 1997, 38,
5427.
(24) Mizuno, N.; Misono, M. Chem. Rev. 1998, 98, 199.
(25) Izumi, C.; Urabe, Y.; Onaka, M. Zeolite, Clay, and
Heteropoly Acid in Organic Reactions; Kodansha Tokyo/
VCH: New York, 1993, Chap. 3.
(26) Preparation of the potassium dodecatangestocobaltate
trihydrate (K5CoW12O40·3 H2O) catalyst, see experimental
and: (a) Habibi, M. H.; Tangestaninejad, S.;
Mahammadpoor-Baltork, I.; Mirkhani, V.; Yadollahi, B.
Tetrahedron Lett. 2001, 42, 2851. (b) Habibi, M. H.;
Tangestaninejad, S.; Mahammadpoor-Baltork, I.; Mirkhani,
V.; Yadollahi, B. Tetrahedron Lett. 2001, 42, 6771.
(27) Garner, P.; Park, J. M. Org. Synth. 1992, 70, 18.
(28) All the products were characterized by mp, IR, 1H NMR and
mass spectral data. Selected analytical data for some
compounds (entry 4), see experimental: Price, C. C.; Hori,
M.; Parasaran, T.; Polk, M. J. Am. Chem. Soc. 1963, 85,
2278.
References
(1) Greene, T. G.; Wuts, P. G. M. Protective Groups in Organic
Synthesis, 2nd ed.; Wiley: New York, 1991, 175–223.
(2) Shriner, R. L.; Fuson, R. C.; Curtin, D. Y.; Morrill, T. C. The
Systematic Identification of Organic Compounds, 6th ed.;
Wiley: New York, 1980.
(3) Donaruma, L. G.; Heldt, W. Z. Org. React. 1960, 11, 1.
(4) Lartey, P. A.; Faghih, R. Recent Progress in the Chemical
Modification of Erythromycin, In Recent Progress in the
Chemical Synthesis of Antibiotics and Related Microbial
Products, Vol. 2; Lukacs, G., Ed.; Springer: Berlin, 1993,
121–140.
(5) (a) Barton, D. H. R.; Beaton, J. M.; Geller, L. E.; Pechet, M.
M. J. Am. Chem. Soc. 1961, 83, 4076. (b) Barton, D. H. R.;
Beaton, J. M.; Geller, L. E.; Pechet, M. M. J. Am. Chem. Soc.
1961, 83, 4083.
(6) Maloney, J. R.; Lyle, R. E.; Scavedra, J. E.; Lyle, G. G.
Synthesis 1978, 212.
(7) Drabowicz, J. Synthesis 1980, 125.
(8) Rao, C. G.; Radhakrishna, A. S.; Singh, B. B.; Bhatnagar, S.
P. Synthesis 1983, 808.
(9) Curran, D. P.; Brill, J. F.; Rakiewicz, D. M. J. Org. Chem.
1984, 49, 1654.
Synthesis 2003, No. 12, 1883–1885 © Thieme Stuttgart · New York