´
I. Favier, F. Giulieri, E. Dun˜ach, D. Hebrault, J. R. Desmurs
FULL PAPER
1,2-(α-hydroxy-γ-butyrolactone),[26] 3,5-di-tert-butyl-4-hydroxyben-
zoic acid,[27] 3,5-di-tert-butyl-4-hydroxybenzaldehyde.[28]
intermediates that further evolve towards the selective alde-
hyde formation.[23]
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R. A. Abramowitch, D. H. Barton, J. P. Finet, Tetrahedron
The oxidation of mandelic acid derivatives can be carried
out by a novel catalytic system based on the use of metallic
bismuth in DMSO/O2 systems. We have shown that that the
nature of the substituents on the aromatic ring may very
strongly determine the chemoselectivity of the process as
well as the reaction rate.
[5]
[6]
With the Bi0 catalytic system, the formation of benzal-
dehyde derivatives is highly favoured with substrates bear-
ing hydroxyl substituents at the 2- or 4-positions of the aro-
matic ring. The presence of an OH group at these positions
has a much stronger directing effect than the other substitu-
ents.
The oxidation of mandelic acids with electron-with-
drawing substituents allows the clean and selective prepara-
tion of the corresponding benzoic acids. The reaction is
proposed to take place through the intermediate formation
of α-keto acids.
Electron-donor groups as substituents on the aromatic
ring of mandelic acid, such as methoxy, direct the oxidation
reaction towards less selective mixtures of aldehyde and
carboxylic acid.
More mechanistic insight is needed for a more complete
understanding of the factors controlling the selectivity of
this oxidation reaction.
[7]
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T. Zevaco, E. Dun˜ach, M. Postel, Tetrahedron Lett. 1993,
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See for example:
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[18a]
P Maggioni, F.Minisci, BE 85,993, 1979
[18b]
(to Brichima S.P.A.), CA 95:42661h.
A. Schouteeten, Y.
Christidis, J. C. Vallejos, EP 81-401352, 1981 (to Hoechst), CA
96:217481z. [18c] T. Shirai, T. Sakurai, JP 4122, 1958 (to Nippon
Experimental Section
[18d]
Kagaku Co.), CA 53:2722p.
U. Sumio, T. Nagaaki, E.
Takuji, S. Yasushi, N. Takahito, JP 77-133091, 1977 (to Ube
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The commercially available products were used without further
purification.
[19]
[20]
K. Bauer, P. Garbe, in Common Fragance and Flavor Materials,
Preparation, Properties and Uses, VCH, Lausanne, 1985.
M. Higuchi, I. Ikeda, T. Hirao, J. Org. Chem. 1997, 62,
1072Ϫ1078.
HPLC analysis was effected with a Waters Millipore apparatus. The
eluent was a mixture of H2O and MeOH (80:20) with H3PO4
(0.5%). The elution was made at 1 mL/min in an isocratic mode.
The products were detected by UV at λ ϭ 220 nm. The HPLC
column was a µ-Bondapack C18 Waters 9 µm (30 cm ϫ 3.9 mm).
[21] [21a]
T. J. Kemp, W. A. Waters, J. Chem. Soc. 1964,
[21b]
1192Ϫ1194.
49, 649Ϫ653.
J. M. Pink, R. Stewart, Can. J. Chem. 1971,
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[22b]
1174Ϫ1779.
S. N. Mahapatro, A. K. Panigrahi, R. Panda,
The reactions were carried out under atmospheric pressure of mo-
lecular oxygen. Mandelic acid or its derivatives (1؊16a) (2 mmol),
was dissolved in DMSO (5 mL) in the presence of Bi0 powder
(0.2 mmol). The mixture was stirred at 125 °C until consumption
D. M. Patro, Inorg. Chem. 1984, 23, 4119Ϫ4120.
[23]
F. Taran, P. Y. Renard, H. Bernard, C. Mioskowski, Y. Frobert,
P. Pradelles, J. Grassi, J. Am. Chem. Soc. 1998, 120,
3332Ϫ3339.
1
[24]
[25]
[26]
of the starting material, which was followed by HPLC and/or H
G. Sartori, G. Casnati, F. Bigi, G. Bonini, Synthesis 1988, 10,
763Ϫ766.
S. Tobita, M. Yamamoto, N. Kurahayashi, R. Tsukagoshi, Y.
Nakamura, J. Phys. Chem. A 1998, 102, 5206Ϫ5214.
A. V. Kalinin, M. A. J. Miah, S. Chattopadhyay, M. Tsukazaki,
M. Wicki, T. Nguen, A. L. Coelho, M. Kerr, V. Snieckus, Syn-
lett 1997, 7, 839Ϫ841.
NMR spectroscopy. The crude reaction mixture was hydrolysed
with 5 mL of an aqueous 1 HCl solution saturated with NaCl,
and extracted with ethyl acetate (5 ϫ 10 mL). The organic phases
were collected and washed twice with an aqueous 0.1 HCl solu-
tion saturated with NaCl, dried over MgSO4 and filtered off. The
1
products were analysed and quantified by HPLC and by H NMR
[27]
[28]
J. Adams, J. Org. Chem. 1967, 32, 3992Ϫ3996.
W. Baik, H. J. Lee, J. M. Jang, S. Koo, B. H. Kim, J. Org.
Chem. 2000, 65, 108Ϫ115.
spectroscopy, and their spectroscopic data compared to those of
authentic samples. Compounds 1aϪ16a, 1bϪ11b, 14bϪ16b,
1cϪ11c and 14cϪ16c are commercially available. The other com-
pounds are reported in the literature: 13b,[24] 13c,[25] naphthalen-
Received January 8, 2002
[O02009]
1988
Eur. J. Org. Chem. 2002, 1984Ϫ1988