Oxidation of benzyl alcohols with Oxone and sodium bromide

Article abstract of DOI:10.1081/SCC-120005418

Reaction of benzyl alcohols with Oxone and sodium bromide in aqueous acetonitrile gave the corresponding benzaldehydes in excellent yields. However, electron-rich benzyl alcohols afforded ring bromination products via bromodecarbonylation of the resulting benzaldehydes.

Full text of DOI:10.1081/SCC-120005418

This article was downloaded by: [Pennsylvania State University]
On: 11 July 2012, At: 23:13
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK
Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic
Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
OXIDATION OF BENZYL ALCOHOLS WITH OXONE® AND
SODIUM BROMIDE
Bon-Suk Koo a , Chang Keun Lee a & Kee-Jung Lee b
a Department of Industrial Chemistry, Hanyang University, Seoul, 133-791, Korea
b Department of Industrial Chemistry, Hanyang University, Seoul, 133-791, Korea
Version of record first published: 18 Oct 2011
To cite this article: Bon-Suk Koo, Chang Keun Lee & Kee-Jung Lee (2002): OXIDATION OF BENZYL ALCOHOLS WITH OXONE®
AND SODIUM BROMIDE, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic
Chemistry, 32:14, 2115-2123
To link to this article: http://dx.doi.org/10.1081/SCC-120005418
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to
anyone is expressly forbidden.
The publisher does not give any warranty express or implied or make any representation that the contents
will be complete or accurate or up to date. The accuracy of any instructions, formulae, and drug doses should
be independently verified with primary sources. The publisher shall not be liable for any loss, actions, claims,
proceedings, demand, or costs or damages whatsoever or howsoever caused arising directly or indirectly in
connection with or arising out of the use of this material.

SYNTHETIC COMMUNICATIONS
Vol. 32, No. 14, pp. 2115–2123, 2002
OXIDATION OF BENZYL ALCOHOLS
WITH OXONEÕ AND SODIUM BROMIDE
*
Bon-Suk Koo, Chang Keun Lee, andKee-Jung Lee
Department of Industrial Chemistry,
Hanyang University, Seoul 133-791, Korea
ABSTRACT
Reaction of benzyl alcohols with OxoneÕ and sodium bro-
mide in aqueous acetonitrile gave the corresponding benzal-
dehydes in excellent yields. However, electron-rich benzyl
alcohols afforded ring bromination products via bromodecar-
bonylation of the resulting benzaldehydes.
Key Words: Oxidation; Benzyl alcohols; OxoneÕ; Sodium
bromide
The selective oxidation of benzylic alcohols to benzaldehydes is a
transformation of considerable importance in organic synthesis. Whilst
numerous reagents have been developed to effect this process, many of
them use greater than stoichiometric quantities of toxic heavy metals or
co-oxidants which severely handicap their applicability to large scale indus-
trial processes.[1,2] Also, the oxidation of organic compounds by hypohalite
salts or halogen is well known method in organic synthesis.[3] Especially,
oxidation of primary alcohols to aldehydes with hydrogen peroxide using
methyltrioxorhenium and bromide ions as cocatalysts,[4] and with oxoam-
monium salt and bromide ions[5] have been described.
*Corresponding author. E-mail: leekj@hanyang.ac.kr
2115
DOI: 10.1081/SCC-120005418
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

2116
KOO, LEE, AND LEE
Recent reports have dealt with the use of a triple salt of potassium
peroxymonosulfate, potassium hydrogen sulfate, and potassium sulfate,
which is commercially available as OxoneÕ (2KHSO5ꢀKHSO4ꢀK2SO4), can
be used for the oxidation of alkenes,[6] arenes,[7] amines,[8] imine,[9] sulfides,[10]
selenides,[11] ꢀ-amino acids,[12] and acetals.[13] Also, there are reports in the
literature, where OxoneÕ is a useful oxidation reagent of alcohols and alde-
hydes. Examples include the conversions of 2-propanol to acetone,[6] ethanol
to ethyl acetate,[6] and benzaldehyde to benzoic acid.[6,14] Another example is
the oxidation of secondary alcohols to ketones in the presence of wet-
aluminium oxide in aprotic solvents.[15] Also, Bolm and co-workers have
demonstrated that the combination of TEMPO/OxoneÕ/Bu4NBr is an effec-
tive system for the oxidation of alcohols to aldehydes and ketones, including
benzylic ones.[16] Moreover, the use of OxoneÕ and aqueous sodium halides
was conducted as a convenient halogenating reagent to achieve oxidation of
ꢀ,ꢁ-enones,[17] bromination of pyrimidines,[18] and halogenation of
toluene.[6]
In previous paper, we have shown that sodium bromide combined
with OxoneÕ serves as effective bromodecarboxylation reagent of various
cinnamic acids[19] and halogenation of aromatic methyl ketones.[20] In the
course of our study to extend the scope of the OxoneÕ/NaBr reagent in
organic synthesis, we have found that this reagent facilitates the oxidation
of benzylic alcohols to benzaldehydes satisfactorily.
Optimization of the reaction conditions revealed that simple stirring a
solution of benzyl alcohol (1 equivalent), OxoneÕ (1 equivalent) and sodium
bromide (2 equivalent) in a 1 : 1 mixture of CH3CN/H2O effected the for-
mation of benzaldehyde in 87% isolated yield within 3 h. However, in the
absence of sodium bromide, the reaction did not proceed at all in 24 h at r.t.
Further studies showed that this oxidation method could be applied to a
wide range of benzylic alcohols and representative primary and secondary
alcohols as shown in Table 1. They are all known compounds and are
1
identified by their IR, H NMR and mass spectral data.
A plausible mechanism of the oxidation is shown in Scheme 1 based on
literatures. The oxidation of bromide ion by peroxymonosulfate ion would
Scheme 1.

BENZYL ALCOHOLS WITH OXONEÕ AND SODIUM BROMIDE
2117
Table 1. Oxidation of Alcohols with OxoneÕ and NaBr
Entry
1
Substrate
Time (h)
3
Product
No.
Yield (%)a
87
1
2
3
4
5
2
3
2
3
4
93
96
24
1
20b
22
5a
5b
5c
44
14
6
1
6a
6b
7
63
20
7
8
3
99
99
0.5
8
9
9
1
91
80
17
10
0.5
10a
10b
1
aYields are based on isolated products, characterized by IR, H NMR and GC-MS
spectra.
b65% alcohol was recovered.

2118
KOO, LEE, AND LEE
give the hypobromous acid[16,21] and subsequent oxidation of alcohols
affords aldehydes and ketones.
The presence of electron-donating groups in the aromatic ring has little
influence on the oxidation rates but these are markedly lowered by intro-
ducing a strong electron-acceptor group. Thus, p-nitrobenzyl alcohol was
oxidized to aldehyde in only 20% yield over 24 h. Also, the reaction was
unsuccessful for electron-rich arene such as p-methoxybenzyl alcohol,
which presumably suffered complications due to competing bromodecarbo-
nylation of the resulting p-anisaldehyde which was accompanied by the for-
mation of 4-bromoanisole (44%) and 2,4-dibromoanisole (14%).[22]
Similarly, p-acetamidobenzyl alcohol gave bromodecarbonylation products,
4-bromoacetanilide (63%) and 2,4-dibromoacetanilide (20%).[22] In the
oxidation of 1-phenyl-1,2-ethanediol, the secondary benzylic alcoholic
function was oxidized with high selectivity to form 2-hydroxyacetophenone
in 99% yield. The oxidation of secondary alcohols afforded the correspond-
ing ketones in excellent yields. But, primary alcohol such as 1-pentanol was
converted mainly into the dimeric ester, pentyl valerate, presumably via hemi-
acetal intermediate.[23]
In conclusion, we developed a simple oxidation method of benzyl
alcohols to benzaldehydes with OxoneÕ/NaBr in aqueous acetonitrile
under the mild conditions. This method provides an alternative, facile
preparation of benzaldehydes, since OxoneÕ and sodium bromide are
cheap, nontoxic, stable, and easy to handle.
EXPERIMENTAL
Melting points were determined in open capillaries with an
Electrothermal melting point apparatus and are uncorrected. Progress of
reactions were followed by TLC using silica gel with fluorescent indicator
coated on aluminium sheets. Infrared spectra were recorded on a Nicolet
1
Magna 550 FTIR spectrometer and H NMR spectra were measured on a
Varian Gemini 300 spectrometer in CDCl3 using TMS as an internal
standard. Mass spectra were obtained on a ThermoQuest Polaris Q mass
spectrometer operating at 70 eV.
General Procedure for the Oxidation of Alcohols with OxoneÕ
and Sodium Bromide
To a stirred solutions of alcohols (3 mmol) in aqueous CH3CN (30 mL,
1 : 1 by volume) was added NaBr (0.62 g, 6 mmol) and OxoneÕ (1.84 g,

BENZYL ALCOHOLS WITH OXONEÕ AND SODIUM BROMIDE
2119
3 mmol). Reactions were continuously monitored by thin-layer chromato-
graphy and stirred at r.t. for the time indicated in Table 1. The reaction
mixture was quenched with aqueous sodium thiosulfate, and extracted with
ether (3 ꢁ 30 mL). The combined organic layers were washed with water,
dried over anhydrous MgSO4, filtered, and concentrated in vacuo. The
residue was chromatographed on a silica gel column and eluted with
hexane–EtOAc 10 : 1 to give the products (Table 1).
Analytical Data for the Products
1: Liquid (Lit.[24] b.p. 178ꢂC). IR (neat) cmꢃ1: 1701, 1600, 1460, 1312,
1
1204, 827, 749; H NMR ꢂ 7.45–7.67 (m, 3H), 7.87–7.90 (m, 2H), 10.02
(s, 1H); MS m/z (rel. intensity) 106 (Mþ, 34), 105 (74), 77 (100), 51 (22).
2: M.p. 47–49ꢂC (Lit.[24] 47.5ꢂC). IR (KBr) cmꢃ1: 1697, 1576, 1479,
1
1386, 1204, 1013, 811, 539, 477; H NMR ꢂ 7.53 (d, J ¼ 8.5 Hz, 2H), 7.83
(d, J ¼ 8.5 Hz, 2H), 9.99 (s, 1H); MS m/z (rel. intensity) 142 (Mþ, 17), 141
(58), 140 (Mþ, 46), 139 (100), 113 (7), 111 (19), 77 (6), 75 (13).
3: Liquid (Lit.[24] b.p. 204–205ꢂC). IR (neat) cmꢃ1: 1701, 1607, 1386,
1308, 1207, 1169, 847, 808; 1H NMR ꢂ 2.43 (s, 3H), 7.33 (d, J ¼ 7.9 Hz, 2H),
7.78 (d, J ¼ 7.9 Hz, 2H), 9.97 (s, 1H); MS m/z (rel. intensity) 120 (Mþ, 40),
119 (100), 91 (72), 65 (28).
4: M.p. 103–105ꢂC (Lit.[24] 106ꢂC). IR (KBr) cmꢃ1: 1712, 1607, 1538,
1
1344, 1293, 1196, 854, 819, 738; H NMR ꢂ 8.08 (d, J ¼ 8.5 Hz, 2H), 8.41
(d, J ¼ 8.5 Hz, 2H), 10.17 (s, 1H); MS m/z (rel. intensity) 151 (Mþ, 44), 150
(100), 77 (13), 51 (16).
5a: Liquid (Lit.[24] b.p. 249.5ꢂC). IR (neat) cmꢃ1: 1685, 1600, 1507,
1
1312, 1262, 1161, 1025, 834; H NMR ꢂ 3.90 (s, 3H), 7.01 (d, J ¼ 8.5 Hz,
2H), 7.85 (d, J ¼ 8.5 Hz, 2H), 9.90 (s, 1H); MS m/z (rel. intensity) 136 (Mþ,
60), 135 (100), 107 (20), 92 (9), 77 (42), 63 (14).
5b: Liquid (Lit.[24] b.p. 215ꢂC). IR (neat) cmꢃ1: 1577, 1487, 1289, 1239,
1
1172, 1033, 823; H NMR ꢂ 3.77 (s, 3H), 6.78 (d, J ¼ 8.9 Hz, 2H), 7.37
(d, J ¼ 8.9 Hz, 2H); MS m/z (rel. intensity) 188 (Mþ, 98), 186 (Mþ, 100),
173 (31), 171 (30), 145 (23), 143 (26), 77 (31), 63 (47).
5c: M.p. 61–62ꢂC (Lit.[25] 61–63ꢂC). IR (KBr) cmꢃ1: 1576, 1475, 1378,
1
1263, 1052, 807, 679, 617; H NMR ꢂ 3.87 (s, 3H), 6.77 (d, J ¼ 8.8 Hz, 1H),
7.37 (dd, J ¼ 8.8, 2.3 Hz, 1H), 7.66 (d, J ¼ 2.3 Hz, 1H); MS m/z (rel. inten-
sity) 268 (Mþ, 35), 266 (Mþ, 75), 264 (Mþ, 42), 253 (9), 251 (18), 249 (20),
225 (16), 223 (35), 221 (16), 172 (15), 170 (14), 63 (100).
6a: M.p. 165–167ꢂC (Lit.[24] 168ꢂC). IR (KBr) cmꢃ1: 3293, 1677, 1603,
1
1526, 1483, 1394, 1305, 1254, 1013, 823, 737, 504; H NMR ꢂ 2.04 (s, 3H),

2120
KOO, LEE, AND LEE
7.47 (d, J ¼ 8.9 Hz, 2H), 7.56 (d, J ¼ 8.9 Hz, 2H), 10.07 (s, 1H); MS m/z (rel.
intensity) 215 (Mþ, 43), 213 (Mþ, 43), 173 (96), 171 (100), 92 (96), 65 (41).
6b: M.p. 142–143ꢂC (Lit.[26] 144.7ꢂC). IR (KBr) cmꢃ1: 3289, 1658,
1
1572, 1522, 1460, 1367, 1293, 1040, 831, 602, 547; H NMR ꢂ 2.24 (s, 3H),
7.42 (dd, J ¼ 8.9, 2.1 Hz, 1H), 7.57 (s, 1H), 7.68 (d, J ¼ 2.1 Hz, 1H), 8.26
(d, J ¼ 8.9 Hz, 1H); MS m/z (rel. intensity) 295 (Mþ, 12), 293 (Mþ, 20), 291
(Mþ, 10), 253 (47), 251 (100), 249 (54), 214 (70), 212 (75), 172 (31), 170 (37),
91 (36), 90 (69), 63 (44).
7: M.p. 79–81ꢂC (petroleum ether) (Lit.[24] 90ꢂC). IR (KBr) cmꢃ1: 3421,
1
1689, 1600, 1456, 1409, 1301, 1231, 1106, 970, 761, 683; H NMR ꢂ 3.51
(t, J ¼ 4.6 Hz, 1H), 4.89 (d, J ¼ 4.6 Hz, 2H), 7.49–7.67 (m, 3H), 7.92–7.95
(m, 2H); MS m/z (rel. intensity) 136 (Mþ, 1), 105 (77), 77 (100), 51 (17).
8: Liquid (Lit.[24] b.p. 202.6ꢂC). IR (neat) cmꢃ1: 1681, 1596, 1448, 1359,
1
1262, 951, 765, 687; H NMR ꢂ 2.60 (s, 3H), 7.43–7.59 (m, 3H), 7.94–7.98
(m, 2H); MS m/z (rel. intensity) 120 (Mþ, 16), 105 (100), 77 (23), 51 (9).
9: Liquid (Lit.[24] b.p. 155.6ꢂC). IR (neat) cmꢃ1: 2939, 1712, 1452,
1304, 1223, 1118, 904; 1H NMR ꢂ 1.73 (m, 2H), 1.85 (m, 4H), 2.34
(dd, J ¼ 7.0, 6.4 Hz, 4H); MS m/z (rel. intensity) 98 (Mþ, 67), 80 (12), 69
(26), 55 (100), 42 (20), 41 (24).
10a: Liquid (Lit.[24] b.p. 203.7ꢂC). IR (neat) cmꢃ1: 1732, 1648,
1
1619, 1262, 1180, 1106; H NMR ꢂ 0.91 (t, J ¼ 6.7 Hz, 3H), 0.92 (t, J ¼
7.3 Hz, 3H), 1.35 (m, 6H), 1.61 (m, 4H), 2.30 (t, J ¼ 7.3 Hz, 2H), 4.06 (t,
J ¼ 6.7 Hz, 2H); MS m/z (rel. intensity) 173 (Mþ þ 1, 64), 172 (Mþ, 3), 103
(100), 85 (70), 75 (33), 70 (86), 57 (80), 55 (79).
10b: Liquid (Lit.[24] b.p. 186ꢂC). IR (neat) cmꢃ1: 2959, 2675, 1712,
1472, 1421, 1277, 1215, 943; 1H NMR ꢂ 0.93 (t, J ¼ 7.3 Hz, 3H), 1.37
(sextet, J ¼ 7.6 Hz, 2H), 1.63 (quintet, J ¼ 7.6 Hz, 2H), 2.35 (t, J ¼ 7.6 Hz,
2H); MS m/z (rel. intensity) 87 (2), 73 (28), 60 (100), 55 (13), no Mþ.
ACKNOWLEDGMENTS
This work was supported by Hanyang University, Korea, made in the
program year of 2001.
REFERENCES
1. (a) Hollingworth, G.J. In Comprehensive Organic Functional Group
Transformations; Katritzky, A.R., Meth-Cohn, O., Rees, C.W.,
Pattenden, G., Eds.; Elsevier Science Ltd.: Oxford, 1995; Vol. 3,

BENZYL ALCOHOLS WITH OXONEÕ AND SODIUM BROMIDE
2121
81–109; (b) Larock, R.C. Comprehensive Organic Transformations; VCH
Publishers, Inc.: New York, 1989; 604–614.
2. (a) Barrett, A.G.M.; Braddock, D.C.; McKinnell, R.M.; Waller, F.J.
Ytterbium(III) Triflate as a Recyclable Catalyst for the Selective Atom
Economic Oxidation of Benzyl Alcohols to Benzaldehydes. Synlett 1999,
(9), 1489–1490; (b) Sato, K.; Takagi, J.; Aoki, M.; Noyori, R. Hydrogen
Peroxide Oxidation of Benzylic Alcohols to Benzaldehydes and Benzoic
Acids Under Halide-Free Conditions. Tetrahedron Lett. 1998, 39(41),
7549–7552; (c) Zondervan, C.; Hage, R.; Feringa, B.L. Selective
Catalytic Oxidation of Benzylic Alcohols to Benzaldehydes with a
Dinuclear Manganese(IV) Complex. Chem. Commun. 1997, (5),
419–420; (d) Barhate, N.B.; Sasidharan, M.; Sudalai, A.; Wakharkar,
R.D. Selective Catalytic Oxidation of Benzylic Alcohols to the
Corresponding Carbonyl Compounds with TBHP over CrS-2.
Tetrahedron Lett. 1996, 37(12), 2067–2070; (e) Feldberg, L.; Sasson, Y.
Copper-Catalysed Oxidation of Hydroxy Compounds by tert-Butyl
Hydroperoxide Under Phase-Transfer Conditions. Chem. Commun.
1994, (15), 1807; (f ) Kaneda, K.; Kawanishi, Y.; Teranishi, S.
Zr-Catalyzed Oxidation of Alcohols to Aldehydes in the Presence of
tBuOOH. High Reactivity for Primary and Allylic Hydroxyl Functions.
Chem. Lett. 1984, (9), 1481–1482; (g) Ogura, F.; Otsubo, T.; Ariyoshi, K.;
Yamaguchi, H. bis( p-Methoxyphenyl)selenoxide as a Cooxidant for
Selenium Dioxide Oxidation of Benzyl Alcohols. Chem. Lett. 1983,
(12), 1833–1834; (h) Kanemoto, S.; Oshima, K.; Matsubara, S.; Takai,
K.; Nozaki, H. Transition-Metal Catalyzed Oxidation of Alcohols to
Aldehydes and Ketones by Means of Me3SiOOSiMe3. Tetrahedron
Lett. 1983, 24(21), 2185–2188; (i) Muller, P.; Godoy, J. Catalyzed
Oxidation of Alcohols and Aldehydes with Iodosylbenzene.
Tetrahedron Lett. 1981, 22(25), 2361–2364.
3. (a) Stevens, R.V.; Chapman, K.T.; Weller, H.N. Convenient and
Inexpensive Procedure for Oxidation of Secondary Alcohols to
Ketones. J. Org. Chem. 1980, 45(10), 2030–2032; (b) Stevens, R.V.;
Chapman, K.T. Further Studies on the Utility of Sodium Hypochlorite
in Organic Synthesis. Selective Oxidation of Diols and Direct Conversion
of Aldehydes to Esters. Tetrahedron Lett. 1982, 23(45), 4647–4650; (c)
Nwaukwa, S.O.; Keehn, P.M. The Oxidation of Alcohols and Ethers
Using Calcium Hypochlorite [Ca(OCl)2]. Tetrahedron Lett. 1982, 23(1),
35–38; (d) Palou, J. Oxidation of Some Organic Compounds by Aqueous
Bromine Solutions. Chem. Soc. Rev. 1994, 23(5), 357–361.
4. Espenson, J.H.; Zhu, Z.; Zauche, T.H. Bromide Ions and Methyl-
trioxorhenium as Cocatalysts for Hydrogen Peroxide Oxidations and
Brominations. J. Org. Chem. 1999, 64(4), 1191–1196.

2122
KOO, LEE, AND LEE
5. Anelli, P.L.; Biffi, C.; Montanari, F.; Quici, S. Fast and Selective
Oxidation of Primary Alcohols to Aldehydes or to Carboxylic Acids
and of Secondary Alcohols to Ketones Mediated by Oxoammonium
Salts Under Two-Phase Conditions. J. Org. Chem. 1987, 52(12),
2559–2562.
6. Kennedy, R.J.; Stock, A.M. The Oxidation of Organic Substances by
Potassium Peroxymonosulfate. J. Org. Chem. 1960, 25(11), 1901–1906.
7. Jeyaraman, R.; Murray, R.W. Production of Arene Oxides by the
Caroate–Acetone System (Dimethyldioxirane). J. Am. Chem. Soc.
1984, 106(8), 2462–2463.
8. Zabrowski, D.L.; Moormann, A.E.; Beck, K.R.J. The Oxidation of
Aromatic Amines in the Presence of Electron-rich Aromatic Systems.
Tetrahedron Lett. 1988, 29(36), 4501–4504.
9. Davis, F.A.; Chattopadhyay, S.; Towson, J.C.; Lal, S.; Reddy, T.
Chemistry of Oxaziridines. 9. Synthesis of 2-Sulfonyl- and 2-Sulfamyl-
oxaziridines Using Potassium Peroxymonosulfate (Oxone). J. Org.
Chem. 1988, 53(9), 2087–2089.
10. Greenhalgh, R.P. Selective Oxidation of Phenyl Sulphides to
Sulphoxides or Sulphones Using OxoneÕ and Wet Alumina. Synlett
1992, (3), 235–236.
11. Ceccherelli, P.; Curini, M.; Epifano, F.; Marcotullio, M.C.;
Rosati, O. Oxone Oxidation of Selenides: A Mild and Efficient
Method for the Preparation of Selenones. J. Org. Chem. 1995,
60(26), 8412–8413.
12. Paradkar, V.M.; Latham, T.B.; Demko, D.M. Oxidative Decarboxyla-
tion of ꢀ-Amino Acids with in-situ Generated Dimethyl Dioxirane.
Synlett 1995, (10), 1059–1060.
13. Curini, M.; Epifano, F.; Marcotullio, M.C.; Rosati, O. OxoneÕ: A
Convenient Reagent for the Oxidation of Acetals. Synlett 1999, (6),
777–779.
14. (a) Webb, K.S.; Ruszkay, S.J. Oxidation of Aldehydes with OxoneÕ in
Aqueous Acetone. Tetrahedron 1998, 54 (3/4), 401–410; (b) Baumstark,
A.L.; Beeson, M.; Vasquez, P.C. Dimethyldioxirane: Mechanism of
Benzaldehyde Oxidation. Tetrahedron Lett. 1989, 30(41), 5567–5570.
15. Hirano, M.; Oose, M.; Morimoto, T. Oxidation of s-Alcohols with
Oxone in Aprotic Solvents in the Presence of Wet-Aluminium Oxide.
Bull. Chem. Soc. Jpn. 1991, 64(3), 1046–1047.
16. Bolm, C.; Magnus, A.S.; Hilderbrand, J.P. Catalytic Synthesis of
Aldehydes and Ketones Under Mild Conditions Using TEMPO/
Oxone. Org. Lett. 2000, 2(8), 1173–1175.
17. Dieter, R.K.; Nice, L.E.; Velu, S.E. Oxidation of ꢀ,ꢁ-Enones and
Alkenes with Oxone and Sodium Halides: A Convenient Laboratory

BENZYL ALCOHOLS WITH OXONEÕ AND SODIUM BROMIDE
2123
Preparation of Chlorine and Bromine. Tetrahedron Lett. 1996, 37(14),
2377–2380.
18. Ross, S.A.; Burrows, C.J. Bromination of Pyrimidines Using Bromide
and Monoperoxysulfate: A Competition Study Between Cytidine,
Uridine and Thymidine. Tetrahedron Lett. 1997, 38(16), 2805–2808.
19. You, H.-W.; Lee, K.-J. Halodecarboxylation of ꢀ,ꢁ-Unsaturated
Carboxylic Acids Bearing Aryl and Styrenyl Group at ꢁ-Carbon
with OxoneÕ and Sodium Halide. Synlett 2001, (1), 105–107.
20. Kim, E.-H.; Koo, B.-S.; Song, C.-E.; Lee, K.-J. Halogenation of
Aromatic Methyl Ketones Using OxoneÕ and Sodium Halide. Synth.
Commun. 2001, 31(23), 3627–3632.
21. Montgomery, R.E. Catalysis of Peroxymonosulfate Reactions by
Ketones. J. Am. Chem. Soc. 1974, 96(25), 7820–7821.
22. Koo, B.-S.; Kim, E.-H.; Lee, K.-J. Bromodecrbonylation and
Bromodecarboxylation of Benzaldehydes and Benzoic Acids with
OxoneÕ and Sodium Bromide. Synth. Commun. 2001, 31(15), in press.
23. Takase, K.; Masuda, H.; Kai, O.; Nishiyama, Y.; Sakaguchi, S.;
Ishii, Y. Oxidative Esterification of Primary Alcohols by NaBrO3/
NaHSO3 Reagents in Aqueous Medium. Chem. Lett. 1995, (10),
871–872.
24. CRC Handbook of Chemistry and Physics; 68th Ed.; Weast, R.C.,
Astle, M.J., Beyer, W.H., Eds.; CRC Press, Inc.: Florida, 1987 C42–
C553.
25. Hazlet, S.E.; Dornfeld, C.A. The Reduction of Aromatic Nitro
Compounds with Activated Iron. J. Am. Chem. Soc. 1944, 66(10),
1781–1782.
26. Owen, G. Freezing-Point Curves of Binary Mixtures of Some
Substituted Acetanilides. J. Chem. Soc. 1923, 123, 3392–3397.
Received in the UKApril 18, 2001