Synthesis of aromatic aldehydes by a fast method involving Kornblum's reaction

Article abstract of DOI:10.1080/00397910802222795

Aromatic aldehydes were synthesized by oxidation of corresponding halides with dimethyl sulfoxide on potassium bicarbonate by microwave irradiation. Short reaction time and high yields were obtained. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910802222795

This article was downloaded by: [McGill University Library]
On: 25 December 2012, At: 10:53
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
Synthesis of Aromatic
Aldehydes by a Fast Method
Involving Kornblum's Reaction
George Bratulescu a
a University of Craiova, Faculty of Chemistry,
Craiova, Romania
Version of record first published: 25 Aug 2010.
To cite this article: George Bratulescu (2008): Synthesis of Aromatic Aldehydes
by a Fast Method Involving Kornblum's Reaction, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 38:16,
2748-2752
To link to this article: http://dx.doi.org/10.1080/00397910802222795
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 Communications1, 38: 2748–2752, 2008
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910802222795
Synthesis of Aromatic Aldehydes by a Fast
Method Involving Kornblum’s Reaction
George Bratulescu
University of Craiova, Faculty of Chemistry, Craiova, Romania
Abstract: Aromatic aldehydes were synthesized by oxidation of corresponding
halides with dimethyl sulfoxide on potassium bicarbonate by microwave
irradiation. Short reaction time and high yields were obtained.
Keywords: Aromatic aldehydes, aryl bromide, DMSO, Kornblum oxidation
INTRODUCTION
The synthesis of aromatic aldehydes by Kornblum’s reaction involves
appropriate primary halides and dimethyl sulfoxide as oxidant.[1,2] This
reaction is widely employed for the synthesis of bifunctional ligands used
in binding radioisotopes of Cu to antibodies,[3] novel polynitrodiols,[4]
optically active and racemic alpha-nitronyl nitroxides,[5] histrionico-
toxin,[6] potential plant-protecting compounds,[7] morphine alkaloids,[8]
asymmetric ligands for use in catalysts,[9] and the prostanoids.[10]
An important disadvantage of the Kornblum aldehyde synthesis by
conventional methods is the long reaction time at room temperature to
acquire good yields.[1,2,11,12] An improvement of this reaction has been
realized by ultrasound.[6] Microwave irradiation has never used to assist
the aldehyde synthesis by Kornblum’s reaction.
Received in the U.K. September 26, 2007
Address correspondence to George Bratulescu, University of Craiova, Faculty
of Chemistry, 13 A.I. Cuza, 200396 Craiova, Romania. E-mail: georgebratulescu@
yahoo.com
2748

Synthesis of Aromatic Aldehydes by a Fast Method
RESULTS AND DISCUSSION
2749
In the classic Kornblum’s reaction, a tertiary amine catalyst is used in a liquid
chemical medium.[11] The primary halides and dimethyl sulfoxide (DMSO)
are strong polar reagents that absorb microwave radiation very well.
In the past,[13,14] we have realized the synthesis of several organic
compounds in a paste medium. During microwave irradiation in this
medium, chemical reactions take place quickly.[14] With this in mind,
we synthesized several aromatic aldehydes from alkyl bromides, DMSO,
and potassium bicarbonate under similar conditions. The reagents were
well mixed to give a paste, which was irradiated with microwaves.
Very high yields of aldehydes were obtained (Scheme 1).
The short irradiation time of a few minutes, the easy experimental
protocol, the purity of the products, and high yields are the principal
advantages of this method (Table 1).
EXPERIMENTAL
Aryl bromide, DMSO, and potassium bicarbonate are commercially
available substances. The synthesized product was identified by thin-layer
chromatography (TLC; silica gel, Et2O), elemental analysis, and IR spec-
tra. Boiling points were measured by distillation. The infrared spectra
were recorded on a thin liquid layer placed between two KBr pellets, with
the help of a Perkin-Elmer 1600 spectrometer. Elemental analyses were
carried out with a Carlo Erba model 1106 apparatus. An Optiquick
Y71 microwave oven operating at 300 W was employed. The temperature
during the microwave irradiation was determined with the help of a Novo
Quick digital thermometer.
To a mixture of aryl bromide (3 mmol) and DMSO (4 mmol), potass-
ium bicarbonate (7 mmol) was added in a 25- mL Erlenmeyer flask. The
mixture was irradiated with microwaves in a microwave oven (k ¼ 12.2 cm)
for the required time. The resulting mixture was poured in 60 mL of ice
water and extracted two times with 50 mL of ether. Evaporation of the sol-
vent gives the product of high chemical purity (Table 1).
Scheme 1. Halide oxidation with DMSO uner microwaves.

2750

Synthesis of Aromatic Aldehydes by a Fast Method
REFERENCES
2751
1. Kornblum, N.; Powers, J. W.; Anderson, G. J.; Jones, W. J.; Larson, H. O.;
Levand, O.; Weaver, W. M. A new and selective method of oxidation. J. Am.
Chem. Soc. 1957, 79, 6562.
2. Kornblum, N.; Powers, J. W.; Anderson, G. J. A new and selective method
of oxidation. The conversion of alkyl halides and alkyl tosilates to aldehydes.
J. Am. Chem. Soc. 1959, 81, 4113–4114.
3. McPherson, D. W.; Umbricht, G.; Knapp, F. F. Jr. Radiolabeling of
protein with radioisotopes of copper using p-carboxyalkylphenylglyoxal
bis-(4N-methylthiosemicarbazone) (TSC) bifunctional chelates. J. Labelled
Compd. Radiopharm. 1990, 28, 877–899.
4. Koppes, W. M.; Sitzmann, M. E.; Adolph, H. G. Synthesis of novel
polynitrodiols. J. Chem. Eng. Data. 1986, 31, 119–123.
5. Shimono, S.; Tamura, R.; Ikuma, N.; Takimoto, T.; Kawame, N.; Tamada,
O.; Sakai, N.; Matsuura, H.; Yamauchi, J. Preparation of 2,3-bis(hydroxy-
amino)-2,3-dimethylbutane by reduction of dinitrobutane with Al=Hg in
aqueous THF. J. Org. Chem. 2004, 69, 475–481.
6. Fitch, R. W.; Luzzio, F. A. Ultrasound in natural products synthesis: appli-
cations to the synthesis of histrionicotoxin via nitroalkanal acetals. Ultrason.
Sonochem. 1997, 4, 99–107.
7. Hanefeld, W.; Wurtz, S. J. Synthesis of potential plant protecting compounds
on the basis of 2,3-dihydrothiazol-2-thione. II: Structural variations derived
from a C4-carbaldehyde function. Prakt. Chem. 2000, 342, 445–458.
8. Evans, D. A.; Mitch, C. H. Studies directed towards the total synthesis of
morphine alkaloids. Tetrahedron Lett. 1982, 23, 285–288.
9. Phat, D. T.; Kagan, H. Nouveaux coordinats bidentes, leur fabrication
et leurs applications. FR 2199756; Apr. 12; 1974; Chem. Abstr. 1975, 82,
22291.
10. Wiel, J. B.; Rouessac, F. A new approach to the synthesis of the prostanoids.
Chem. Commun. 1976, 12, 446–447.
11. Lawrence, N. J Aldehydes and ketones. J. Chem. Soc., Perkin Trans. 1998, 1,
1739–1749.
12. Chandrasekhar, S.; Sridhar, M. A bifunctional approach towards the mild
oxidation of organic halides: 2-dimethylamino-N,N-dimethylaniline N-oxide.
Tetrahedron Lett. 2000, 41, 5423–5425.
13. Bratulescu, G. Cyclisation under the action of the microwaves of the
D-saccaric acid to 2,5-furandicarboxylic acid. Rev. Roum. Chim. 2000, 45,
883–885.
14. Bratulescu, G. Improved method for the synthesis of 1,2,4-triazolo[4,5-a]-
pyrimidin-5-ones. Synthesis 2005, 17, 2833–2834.
15. Meyers, C. Y. Aromatic aldehydes from benzyl alcohols via inorganic
hypochlorite oxidation. J. Org. Chem. 1961, 26, 1046–1050.
16. Kayan, B.; Oezen, R.; Gizir, A. M.; Kus, N. S. Oxidation of toluenes to
aromatic aldehydes with molecular oxygen in subcritical water. Org. Prep.
Proced. Int. 2005, 37, 83–86.

2752
G. Bratulescu
17. Baker, R. R.; Bishop, L. J. The pyrolysis of tobacco ingredients. J. Anal.
Appl. Pyrolysis 2004, 71, 223–311.
18. Huang, Y.; Shen, Y.; Chen, C. Bromodiphenylstibine-mediated oxidation of
benzyl alcohols by bromine. Synthesis 1985, 6–7, 651–652.
19. Smirnova, M. M.; Geiderikh, A. V.; Mochalov, S. S.; Shabarov, Y. S.; Yu, S.
Para-alkyl-substituted phenylcyclopropanes in reaction with dinitrogen
tetroxide. Zh. Org. Khim. 1988, 24, 1189–1195.
20. Clement, H. The Grignard reagent from bromopentamethylbenzene. Bull.
Soc. Chim. 1938, 5, 1011–1020.
21. Sahu, S.; Patel, S.; Mishra, B. Selective oxidation of arylaldoximes by
cetyltrimethylammonium dichromate to arylaldehydes and arylnitriles.
Synth. Commun. 2005, 35, 3123–3126.
22. Koton, M. M. Synthesis of nuclearly halogenated derivatives of styrene. Zh.
Obshch. Khim. 1951, 21, 1843–1847.
23. Babu, M. S.; Rai, K. M. L. Synthesis of aromatic aldehydes via
NiCl2 reduction and hydrolysis of oxazolines. Tetrahedron Lett. 2004, 45,
7969–7970.
24. Nishiguchi, I.; Hirashima, T. Electroorganic synthesis. 4. Facile synthesis of
aromatic aldehydes by direct anodic oxidation of para-substituted toluenes.
J. Org. Chem. 1985, 50, 539–541.
25. Gale, D. J.; Wilshire, J. F. K. Amidomethylation of some N,N-dialkyl-
anilines (Tscherniac-Einhorn reaction). Aust. J. Chem. 1975, 28, 2447–2458.
26. Arnold, R. T.; Webers, J. V.; Dodson, R. M. Steric effect of methylene
groups. VI. J. Am. Chem. Soc. 1952, 74, 368–371.
27. Xia, G. M.; Fang, Q.; Xu, X. G.; Xu, G. B.; Liu, Z. Q. Wang, W. Synthesis
and linear, nonlinear fluorescence of bithiophene derivatives. Huaxue Xuebao
2003, 61, 976–982; Chem. Abstr. 2004, 140, 16622.
28. Fry, J.; Ott, R. A. Aldehydes from nitriles. Formation of N-alkylnitrilium
ions and their reduction to N-alkylaldimines by organosilicon hydrides. J.
Org. Chem. 1981, 46, 602–607.