In the Laboratory

edited by
Green Chemistry Mary M. Kirchhoff
ACS Green Chemistry Institute
Washington, DC 20036

Oxidation of Aromatic Aldehydes Using Oxone W

Rajani Gandhari, Padma P. Maddukuri, and Thottumkara K. Vinod*
Department of Chemistry, Western Illinois University, Macomb, IL 61455; *[email protected]

Discussion of green chemistry principles and practical abundance (8). Precipitation and subsequent easy isolation
demonstrations of the accompanying benefits through imple- by filtration of insoluble products is an added advantage of
mentation of pedagogically useful experiments in the gen- using water. Recently Borhan and co-workers described a con-
eral and organic chemistry curricula are becoming widespread venient procedure for oxidation of aromatic aldehydes using
(1); however, only very few chemistry departments in the Oxone in dimethylformamide (9). Oxone, commercially
country currently have green chemistry laboratory modules available from Aldrich Chemical Company, is a 2:1:1 molar
as independent courses or as accompanying laboratory por- mixture of KHSO5, KHSO4, and K2SO4 and is readily
tions of organic chemistry courses. The Department of soluble in water. Considering the water-solubility and the en-
Chemistry at the University of Oregon, under the leadership vironmentally safe and benign nature of Oxone, we recently
of James Hutchison and Kenneth Doxsee, has established a used this reagent in conjunction with another oxidant for the
viable undergraduate green organic chemistry laboratory cur- oxidation of alcohols to carboxylic acids (10). Through this
riculum that offers a training ground for the undergraduate study we established that Oxone is incapable of oxidizing al-
participants in all aspects of techniques and procedures that cohols to aldehydes but readily oxidizes aldehydes to carboxy-
are part of a full-fledged second-year organic chemistry ex- lic acids. This observation prompted us to believe that a green
perience (2). The Department of Chemistry at the Univer- experimental protocol for the oxidation of aromatic aldehydes
sity of Scranton also offers its students an undergraduate using Oxone in water or a water–ethanol mixture could be
laboratory experience in green chemistry (3). A major factor developed and the isolation of the product should be fea-
impeding the widespread introduction of green chemistry ex- sible through simple filtration of the precipitated product
periments in the organic chemistry laboratory curriculum is obtained upon cooling the reaction mixture.
the unavailability of established experimental procedures and
protocols that cover a wide array of concepts and reactions Mechanism
that are pedagogically relevant for second-year students. This
article describes a convenient protocol for oxidation of alde- A plausible mechanism of oxidation of aldehydes using
hydes in water or a water–ethanol mixture using Oxone, a Oxone is reminiscent of Baeyer–Villiger oxidation and is,
nontoxic and eco-friendly reagent. thus, instructive and conceptually comprehensible to an av-
Oxidation of alcohols to the corresponding carbonyl erage second-year organic chemistry student (Scheme I). Po-
compounds and oxidation of aldehydes as synthetic routes tassium persulfate (KHSO5) present in Oxone is presumed
for carboxylic acids or as a derivatization tool for the identi- to be the active oxidant that generates the peroxyacetal in-
fication of “unknown” aldehydes during the qualitative analy- termediate 1B upon nucleophilic addition to the carbonyl
sis portion of the organic chemistry laboratory curriculum carbon. The energetically favored scission of the weak O⫺O
are common procedures in undergraduate laboratories. Use bond is accompanied by a hydride migration as shown to
of household bleach (sodium hypochlorite, NaOCl) for the produce the oxonium ion intermediate 1C, which subse-
oxidation of alcohols in acetic acid is a well-known experi- quently loses a proton to give the final carboxylic acid prod-
ment highlighting the environmental and health benefits of uct. The preferential migration of H over the phenyl group
using an innocuous reagent such as NaOCl (4) over more from 1B can be justified if one considers the resonance sta-
commonly known and used chromium-based reagents that bilization of 1C versus 1C´, which would be the oxonium
pose both environmental and health risks (5). Oxidation of ion intermediate obtained upon phenyl migration. The ben-
aldehydes to the corresponding carboxylic acids, on the other zylic stabilization available for 1D, the less stable resonance
hand, are commonly carried out using KMnO4 in acidic or contributor of 1C, with an incomplete octet is not a viable
basic media, or K2Cr2O7 in acidic medium or chromic acid stabilization feature for 1D´ as the involvement of π elec-
(6). These heavy metal-based reagents are hazardous and the trons will result in even less stable charge-separated resonance
protocols produce metal wastes that require special handling contributors with the negative charge on carbon, a non-elec-
owing to their toxicities. Considering the pedagogical impor- tronegative atom. A discussion of the preferential migratory
tance of oxidation of aldehydes in an undergraduate labora- aptitude of H over phenyl group can be expected to be part
tory curriculum, it is desirable that greener approaches to the of a detailed laboratory report or could be posed as a pre- or
oxidation of aldehydes to carboxylic acids are developed. postlab question.
Use of innocuous auxiliary reaction components, such
as solvents, reagents, and separation agents, is one of the main Green Chemistry Objectives
principles of green chemistry (7). In this context, the use of
water as a reaction medium provides many advantages, in- This experiment, a green oxidation of aromatic aldehydes
cluding its non-toxicity, non-flammability, low cost, and to the corresponding carboxylic acids, was developed with

852 Journal of Chemical Education • Vol. 84 No. 5 May 2007 • www.JCE.DivCHED.org

 In the Laboratory

Scheme I. Mechanism of oxidation of benzaldehyde to benzoic acid using Oxone.

an understanding that the following green objectives can be

demonstrated to the students: (i) use of water as a viable sol-
vent to conduct oxidation of aldehydes, (ii) use of a water–
ethanol mixture as an alternate and eco-friendly solvent
system for substrates that are completely insoluble in water,
even at elevated temperatures, (iii) use of Oxone, an innocu-
ous oxidizing agent that produces benign byproducts, and
finally, (iv) easy isolation of the carboxylic acid product that
precipitates upon cooling the reaction mixture and a result-
ing avoidance of extraction solvents in the product isolation
procedure.

Experimental Overview
Oxidation of aldehydes using Oxone under both macro-
scale and microscale reaction conditions has been achieved. Figure 1. Structures of the substituted benzaldehydes.
Benzaldehyde, 1, and substituted benzaldehydes 3–7 (Fig-
ure 1) are oxidized to the corresponding carboxylic acids us-
ing this protocol. While the oxidation of benzaldehyde is
conveniently carried out in water, the oxidation of the sub- Experimental Procedure
stituted benzaldehydes is carried out in a water–ethanol mix-
ture (4:1 v兾v). In all cases reported here, the carboxylic acid Benzaldehyde (1.0 g, 9.4 mmol), Oxone (FW = 614.8
products are precipitated along with potassium salts from g mol-1, 7.25 g, 11.8 mmol),1 and water (25 mL) were added
Oxone upon cooling the reaction mixture. Careful washing to a 50-mL round-bottom flask fitted with a reflux condenser
of the isolated solid with ice cold water effects selective dis- and a stir bar. The flask was then carefully lowered into a
solution of inorganic salts from the acid product. It is antici- water bath maintained between 70–80 ⬚C and left stirring at
pated that incorporating this experiment in the organic that temperature for 75 min, during which time the Oxone
chemistry laboratory curriculum would occur during the sec- completely dissolved and the reaction mixture turned light
ond term, by which time students are already trained in re- brown. After the reflux period, without disassembling the
fluxing reactions, separating solids by vacuum filtration, and reflux condenser, the flask was cooled in an ice bath for 15–
recrystallizing products. The experimental procedure was op- 20 min. The precipitated benzoic acid contaminated with
timized so students could successfully carry out the experi- potassium salts was filtered at the pump and washed well with
ment, isolate the product, and characterize the purified ice cold water (20–30 mL). The crude product thus obtained
product through melting point determination and 1H NMR was air dried and weighed. Average yield of the crude prod-
spectroscopy during a three-hour laboratory period. uct ranged from 70–93%. Recrystallization of the crude prod-

www.JCE.DivCHED.org • Vol. 84 No. 5 May 2007 • Journal of Chemical Education 853

 In the Laboratory

uct from hot water gave pure benzoic acid, sharply melting Note
at the expected temperature of 121–122 ⬚C.
Oxidations of substituted benzaldehydes 3–7 are simi- 1. The number of moles of potassium persulfate (the active
larly carried out in a water–ethanol mixture (25 mL, 4:1 v兾v) oxidant) present in the amount of Oxone used is 23.6 mmol, double
as the solvent. Average yields of the crude products varied the amount required for complete oxidation of the aldehyde. Ex-
from 65–90%, depending on the substrate and the extent perimentally it was convenient to use such an excess to ensure com-
and duration of the final cooling step prior to filtration of plete oxidation of the aldehyde thereby making the product isolation
the product. 1H NMR spectra of the crude products in all and purification easy.
cases indicated purity of the isolated product to be greater
than 90%, with the starting aldehyde being the only con- Literature Cited
taminant. Oxidation of the aldehydes using this protocol was
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instructions for the students including prelab and postlab Lett. 2003, 5, 1031–1034.
exercises, and copies of 1H NMR spectra of the crude prod- 10. Thottumkara, A. P.; Bowsher, M. S. Vinod, T. K. Org. Lett.
ucts isolated are available in this issue of JCE Online. 2005, 7, 2933–2936.

854 Journal of Chemical Education • Vol. 84 No. 5 May 2007 • www.JCE.DivCHED.org