NaIO4-DMF: A novel reagent for the oxidation of organic halides to carbonyl compounds

Article abstract of DOI:10.1016/S0040-4039(02)02885-X

NaIO₄-DMF oxidises various primary and secondary halides to the corresponding aldehydes and ketones under mild conditions (150°C/40-60 min) in high yields (70-90%).

Full text of DOI:10.1016/S0040-4039(02)02885-X

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 44 (2003) 1375–1377
NaIO4–DMF: a novel reagent for the oxidation of organic
halides to carbonyl compounds
Sasmita Das,a,* A. K. Panigrahia and Golak C. Maikapb
aDepartment of Chemistry, Ravenshaw College, Cuttack Orissa, India
bDabur Research Foundation, Ghazidabad, UP, India
Received 24 September 2002; revised 18 December 2002; accepted 20 December 2002
Abstract—NaIO4–DMF oxidises various primary and secondary halides to the corresponding aldehydes and ketones under mild
conditions (150°C/40–60 min) in high yields (70–90%). © 2003 Elsevier Science Ltd. All rights reserved.
Oxidation of organic halides to the corresponding car-
bonyl compounds is a well known transformation in
organic synthesis. In 1949, the Hass–Bender reaction
was reported for the oxidation of halides.1 Several
methods have been developed to carry out this
conversion2,3 such as the Sommelet reaction4 which is
limited to benzylic halides, the Krohnke reaction (pyri-
dine followed by p-nitrosodimethylaniline)5 and the
Kornblum reaction (DMSO/NaHCO3)6 which is lim-
ited to active halides and requires very high tempera-
ture. Various amine N-oxides7–9 are also used for this
oxidation. Masaki et al.10 have reported the photooxi-
dation of aryl bromides with mesoporous silica FSM-
16. More recently, 2-dimethylamino-N,N-dimethyl
aniline-N-oxide11 was used for this conversion in high
yield. All the above procedures are limited and required
high temperatures. To circumvent all these obstacles,
we planned to explore the use of NaIO4–DMF for the
oxidation of halides to the corresponding carbonyl
compounds. We wish to report here a new and conve-
nient method for the preparation of aldehydes and
ketones from the corresponding halides.
halomethyl naphthalenes (entries 4, 5 and 6) were also
converted to the corresponding aldehydes in 80–85%
yields. Cinnamyl bromide and chloride (entries 7 and 8)
also gave cinnamaldehyde in 90 and 84% yields in 50
and 55 min, respectively.
Secondary halides gave the corresponding ketones, as
shown in Table 2. For example, cyclohexyl bromide
(Table 2, entry 1) gave cyclohexanone in an 84% yield.
Bromodiphenyl methane was converted to benzophe-
none in 90% yield and chlorodiphenyl methane (Table
2, entry 3) took a little more time but gave benzophe-
none in 80% yield. 9-Bromofluorene (Table 2, entry 4)
give 9-fluorenone in good yield in 45 min.
The behaviour of this reagent towards the a-halocar-
bonyl compounds, i.e. phenacyl bromide was also
examined, but to our surprise benzaldehyde was iso-
lated instead of phenyl glyoxal. Phenacyl bromide
might have undergone the same oxidation (Scheme 1)
as primary halides to give phenyl glyoxal which is
further oxidized to phenylglyoxalic acid which under-
goes decarboxylation to give benzaldehyde (85% yield
based upon GC–MS).
The importance of sodium metaperiodate in organic
synthesis prompted us to examine the behaviour of
sodium metaperiodate and dimethyl formamide on dif-
ferent halogen compounds. Primary and secondary
halides were reacted with NaIO4–DMF to give the
corresponding aldehydes and ketones, respectively. It
was found that different primary halides (Table 1) and
secondary halides (Table 2) gave the corresponding
carbonyl compounds in good yields in short time peri-
ods. Octyl bromide was converted into octanal in an
85% yield (Table 1, entry 1). Benzyl bromide (entry 2)
and a substituted benzyl bromide (entry 3) gave the
corresponding aldehydes in good yields. Different
In conclusion, we have developed a new method to
convert primary and secondary halides to the corre-
sponding aldehydes and ketones, using for the first time
the oxidising property of a mixture of NaIO4 and
DMF.
Typical reaction procedure: Benzyl bromide (0.34 g, 2
mmol) was taken in a round bottom flask along with
sodium metaperiodate (NaIO4) (0.42 g, 2 mmol). The
above mixture was dissolved in 30 ml of N,N-dimethyl
formamide (DMF). The reaction mixture was heated at
reflux. The progress of the reaction was monitored by
thin layer chromatography by comparison with the
* Corresponding author. E-mail: sasmitad@hotmail.com
0040-4039/03/$ - see front matter © 2003 Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(02)02885-X

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S. Das et al. / Tetrahedron Letters 44 (2003) 1375–1377
Table 2. Reactions of secondary halides with NaIO4 and
DMF
Table 1. Reactions of primary halides with NaIO4 and DMF
80%) of benzaldehyde. The formation of benzaldehyde
was further confirmed by the melting point of its 2,4-
dinitrophenylhydrazone derivative.
Acknowledgements
We wish to thank the U.G.C. (New Delhi) for generous
financial support.
starting material (10% ethyl acetate in hexane). The
reaction was completed in 40 min. The reaction mixture
was cooled and treated with 20 ml of water and then
extracted with ether (2×30 ml). The combined ether
layers were dried over anhydrous magnesium sulphate
(MgSO4), then filtered off and concentrated. GLC anal-
ysis of the reaction mixture showed the presence of
benzaldehyde (80%). Purification by column chro-
matography on 60–100 mesh silica gel gave (0.18 g,
References
1. Hass, H. B.; Bender, M. L. J. Am. Chem. Soc. 1949, 7,
1767–1769.
2. Kileny, S. N. In Comprehensive Organic Synthesis; Trost,
B. M.; Ley, S. V., Eds.; Pergamom Press: Oxford, 1991;
Vol. 7, pp. 653–670.
Scheme 1.

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3. Smith, M. B.; March, J. March’s Advanced Organic
Chemistry, 5th ed.; Wiley-Interscience Publication: New
York, 2001; pp. 1535–1536.
7. Franzen, V. Org. Synth. 1973, 5, 872–874.
8. Mukaiyama, S.; Inanga, J.; Yamaguchi, M. Bull. Chem.
Soc. Jpn. 1981, 54, 2221.
9. Suzuki, S.; Onishi, T.; Fujita, Y.; Misawa, H.; Otera, J.
Bull. Chem. Soc. Jpn. 1986, 59, 3287.
10. Itoh, A.; Kodana, T.; Inagaki, S.; Masaki, Y. Org.
4. Larock, R. C. Comprehensive Organic Transformations;
VCH Publication: NewYork, 1989; pp. 599–600.
5. Krohnke, F. Angew. Chem., Int. Ed. 1963, 2, 380–
393.
Lett. 2000, 2, 2455–2457.
11. Chandrasekhar, S.; Sridhar, M. Tetrahedron Lett. 2000,
41, 5423–5425.
6. Kornblum, N.; Jones, W. J.; Anderson, G. J. J. Am.
Chem. Soc. 1959, 81, 4113.