For bromate and persulfate as co-oxidants the same modifi-
cation of procedures as noted above for alcohol oxidations was
followed.
Instrumentation
Infrared spectra were measured on a Perkin-Elmer series 1720
Fourier-transform instrument, Raman spectra on a similar
instrument with Nd-YAG laser excitation, electronic spectra on
a Perkin-Elmer Lambda 3 instrument and H NMR spectra on
a JEOL EX-270 spectrometer. Microanalyses were carried out
by the Microanalytical service at Imperial College.
Large-scale oxidation of benzyl alcohol by cis-[OsO4-
(OH)2]2Ϫ–BrO3Ϫ. Benzyl alcohol (5.5 g, 50 mmol) was added to
a cis-[OsO4(OH)2]2Ϫ–BrO3Ϫ solution (500 cm3) prepared by add-
ing OsO4 (0.5 g, 2 mmol) to 500 cm3 of 1 NaOH containing
NaBrO3 (15 g, 100 mmol). The reaction mixture was stirred for
5 h at room temperature and then extracted with diethyl ether
(10 × 25 cm3) to remove unreacted benzyl alcohol. The alkaline
aqueous layer was acidified with 2 H2SO4 to pH 2 and
Na2SO3 (2 g) was added to this layer to remove the osmium, and
also to prevent interference by bromine by-products with the
benzoic acid so formed. It was then extracted with diethyl ether
(10 × 25 cm3) and dried over anhydrous MgSO4 to yield benzoic
acid (5.2 g, 85%).
1
Acknowledgements
We thank Shell Research UK Ltd. and the EPSRC for a CASE
award (to A. J. B.), the British Council for support under the
LINK scheme (to M. G. B.), the Egyptian Ministry of Educa-
tion for support (to A. G. F. S.), and the Wolfson Foundation
and the EPSRC for the X-ray diffractometers. We thank Dr. J. J.
Jolliffe for the analytical data, the University of London Inter-
collegiate Research Service (ULIRS) for the Raman spec-
trometer and Johnson Matthey plc for loans of osmium
tetraoxide.
General procedure for oxidation of aldehydes using cis-
[OsO4(OH)2]2Ϫ–[Fe(CN)6]3Ϫ
.
References
The oxidation of benzaldehyde is typical. To a 1 NaOH solu-
tion (50 cm3) containing K3[Fe(CN)6] (9.9 g, 30 mmol) was
added OsO4 (0.02 g, 0.08 mmol) in water (3 cm3). The mixture
was stirred for 10 min until all solids dissolved and benzalde-
hyde (0.212 g, 2 mmol) was added with stirring for 3 h. The
reaction mixture was extracted with diethyl ether (3 × 25 cm3)
to remove unreacted benzaldehyde. The alkaline aqueous layer
was acidified with 2 H2SO4 to pH 2, Na2SO3 (2 g) was added
to the acidified aqueous layer to remove the osmium, filtered,
and the filtrate extracted with diethyl ether (3 × 25 cm3) and
dried over anhydrous MgSO4 to yield the acid.
1 Part 16, A. J. Bailey, L. D. Cother, W. P. Griffith and D. M. Hankin,
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For bromate and persulfate as co-oxidants the same modifi-
cation of procedures as noted above for alcohol oxidations was
followed.
6 M. Minato, K. Yamamoto and J. Tsuji, J. Org. Chem., 1990, 55, 766.
7 H.-S. Byun, E. R. Kumar and R. Bittman, J. Org. Chem., 1994, 59,
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General procedure for the oxidation of alkyl halides using cis-
[OsO4(OH)2]2Ϫ–[Fe(CN)6]3Ϫ
The oxidation of benzyl bromide is typical. To a 1 NaOH
solution (50 cm3) containing K3[Fe(CN)6] (9.9 g, 30 mmol) was
added OsO4 (0.02 g, 0.08 mmol) in water (3 cm3). The mixture
was stirred for 10 min until all solids had dissolved and benzyl
bromide (0.314 g, 2 mmol) was added with stirring, for 3 h. The
reaction mixture was extracted with diethyl ether (3 × 25 cm3)
to remove unreacted benzyl bromide. The alkaline aqueous
layer was acidified with 2 H2SO4 to pH 2, Na2SO3 (2 g) was
added to the acidified aqueous layer to remove the osmium,
filtered, and the filtrate extracted with diethyl ether (3 × 25 cm3)
and dried over anhydrous MgSO4 to yield the acid.
For bromate as co-oxidant the same modification of pro-
cedures as noted above for alcohol oxidations was followed.
15 D. W. Patrick, L. K. Truesdale, S. A. Biller and K. B. Sharpless,
J. Org. Chem., 1978, 43, 2628.
Oxidation of alkenes
16 G. Wilkinson, B. Hussain-Bates, M. B. Hursthouse, J. Arnold and
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18 R. Jin, C. S. Cho, L. H. Jiang and S. C. Shim, J. Mol. Catal., 1997,
116, 343.
The oxidation of styrene was typical (a modification of that
reported by Sharpless and co-workers40 ). Osmium tetraoxide
(0.01 g, 0.04 mmol) was dissolved in 0.1 KOH (30 cm3) and
the solution became orange indicating the formation of cis-
[OsO4(OH)2]2Ϫ. Dihydroquinidine 4-chlorobenzoate (0.93 g, 2
mmol), K3[Fe(CN)6] (3.96 g, 12 mmol) and styrene (0.42 g, 4
mmol) in tert-butyl alcohol (30 cm3) were added to this
solution. The reaction mixture was stirred at room temperature
for 24 h after which time it was concentrated to dryness in
vacuo. The residue was extracted with diethyl ether (3 × 25 cm3)
and dried over anhydrous MgSO4. The ether was removed in
vacuo to yield a white solid, identified by its melting point and
1H NMR spectrum.
19 R. B. Brown, M. M. Wilkinson and C. L. Hill, Inorg. Chem., 1987,
26, 1602.
20 L. Tschugaev and E. Fritzmann, Z. Anorg. Chem., 1938, 172, 213;
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L. Tschugaev, C. R. Acad. Sci (Paris), 1918, 167, 162.
21 N. N. Nevskii, B. Ivanov-Emin and N. A. Nevskaya, Dokl. Akad.
Nauk SSSR, 1982, 266, 628.
22 N. N. Nevskii, B. Ivanov-Emin, N. A. Nevskaya and N. V. Belov,
Dokl. Akad. Nauk SSSR, 1982, 266, 1138.
23 W. P. Griffith, J. Chem. Soc., 1964, 245.
The same procedure as above but using 1 in place of 0.1
base, followed by acidification in the manner described above
for oxidation of alcohols, gave benzoic acid.
24 W. P. Griffith, J. Chem. Soc. A 1969, 211.
25 H. C. Jewiss, W. A. Levason, M. Tajik, M. Webster and N. P. C.
Walker, J. Chem. Soc., Dalton Trans., 1985, 199.
J. Chem. Soc., Dalton Trans., 1997, Pages 3245–3250
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