γ-picolinium chlorochromate (γ-PCC): A new and efficient reagent for the oxidation of primary and secondary alcohols

Article abstract of DOI:10.1081/SCC-100104013

The preparation of γ-picolinium chlorochromate as a new and efficient reagent for the oxidation of primary and secondary alcohols to their corresponding carbonyl compounds in dichloromethane at ambient temperature is described.

Full text of DOI:10.1081/SCC-100104013

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γ-PICOLINIUM
CHLOROCHROMATE (γ-PCC): A
NEW AND EFFICIENT REAGENT
FOR THE OXIDATION OF
PRIMARY AND SECONDARY
ALCOHOLS
Mohammad Mehdi Khodaie a , Peyman Salehi b &
Maryam Goodarzi a
a Department of Phytochemistry , Medicinal Plants
Research Institute, Shahid Beheshti University ,
Tehran, Iran
b Department of Phytochemistry , Medicinal Plants
Research Institute, Shahid Beheshti University ,
Tehran, Iran
Published online: 09 Nov 2006.
To cite this article: Mohammad Mehdi Khodaie , Peyman Salehi & Maryam
Goodarzi (2001) γ-PICOLINIUM CHLOROCHROMATE (γ-PCC): A NEW AND EFFICIENT
REAGENT FOR THE OXIDATION OF PRIMARY AND SECONDARY ALCOHOLS, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 31:8, 1253-1256, DOI: 10.1081/SCC-100104013
To link to this article: http://dx.doi.org/10.1081/SCC-100104013

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SYNTHETIC COMMUNICATIONS, 31(8), 1253–1256 (2001)
c-PICOLINIUM CHLOROCHROMATE
(c-PCC): A NEW AND EFFICIENT REAGENT
FOR THE OXIDATION OF PRIMARY
AND SECONDARY ALCOHOLS
Mohammad Mehdi Khodaie,* Peyman Salehi,*
and Maryam Goodarzi
Department of Phytochemistry, Medicinal Plants Research
Institute, Shahid Beheshti University, Tehran, Iran
ABSTRACT
The preparation of ꢀ-picolinium chlorochromate as a
new and efficient reagent for the oxidation of primary and
secondary alcohols to their corresponding carbonyl com-
pounds in dichloromethane at ambient temperature is
described.
After 24 years since the introduction of pyridinium chlorochromate as
a reagent for the oxidation of primary and secondary alcohols,1 many chloro-
chromate derivatives have been reported for the oxidative transformation of
organic functional groups.2–8 However, there is an increasing interest for the
preparation of different substituted ammonium chlorochromates with
higher efficiency and lower toxicity.
This letter reports the preparation and synthetic potential of ꢀ-
picolinium chlorochromate (4-methylpyridinium chlorochromate) for the
* Corresponding authors.
1253
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

1254
KHODAIE, SALEHI, AND GOODARZI
oxidation of primary and secondary alcohols. ꢀ-Picoline is a commercially
available compound that is less toxic than pyridine in some respects.9 The
oxidant is stable and can be stored in air for several months without any loss
of its reactivity.
Oxidation reactions were easily achieved by stirring the oxidant with
alcohol in dichloromethane at room temperature (Scheme, Tab.). Benzyl
alcohol and its derivatives with electron-releasing and electron-withdrawing
groups were oxidized and the products were isolated in good to excellent
yields (Tab, entries 1–4). Cyclic model compounds were also oxidized to
their corresponding ketones (Tab., entries 7–9). For the oxidation of cyclo-
dodecanol and 2-adamantol, 1.5 molar equivalents of the reagent were con-
sumed. Similar conditions were also used for the oxidation of linear primary
and secondary alcohols (Tab., entries 10,11).
Scheme 1.
In all reactions, 1 to 1.5 molar equivalents of the oxidant were con-
sumed, which shows the efficiency of the reagent and is an advantage of ꢀ-
PCC in comparison with some other chlorochromate derivatives. Mildness
of reaction condition, ease of work-up procedure, stability of the reagent,
and high yield of products are among the other advantages of this method,
which make ꢀ-picolinium chlorochromate a benchtop and versatile reagent
for the oxidation of primary and secondary alcohols.
EXPERIMENTAL
All of the products are known compounds and were characterized by
comparison of their spectral data (1H NMR, IR) and physical properties
with those of authentic samples. The purity determination of substrates and
reaction monitoring were accomplished by TLC using silica gel polygram
SIL G/UV 254 plates. All yields refer to isolated products.

c-PICOLINIUM CHLOROCHROMATE
1255
Table 1. Oxidation of Primary and Secondary Alcohols by ꢀ-Picolinium
Chlorochromate at Room Temperature
Oxid./Sub. Time Yield
(mole ratio) (min) (%)
Entry
Alcohol
Product
1
2
3
1
1
1
20
10
45
75
70
61
4
5
6
1
1
1
90
20
15
92
92
98
7
8
9
1.5
1.5
1
75
95
80
92
150
120
10
11
CH3(CH2)5CH2OH
1.5
1.5
180
180
65
70
CH3(CH2)5CHO
CH3(CH2)4CHOH(CH3)
CH3(CH2)4COCH3
12
1
15
85

1256
KHODAIE, SALEHI, AND GOODARZI
Preparation of c-Picolinium Chlorochromate
Chromium trioxide (3 g) was dissolved in hydrochloric acid (19%,
5.8 mL) in a beaker cooled in ice. ꢀ-Picoline (2.8 mL) was added in small
portions with stirring over 5 min. The mixture was stirred and warmed to
room temperature for 5 h and concentrated at reduced pressure. The brown
crystalline ꢀ-PCC was precipitated after cooling the mixture in 90% yield.
General Procedure for the Oxidation of Alcohols with c-PCC
ꢀ-Picolinium chlorochromate (1–1.5 mmol) was added to a solution of
alcohol (1 mmol) in dichloromethane (5 mL). The progress of reaction was
followed by thin layer chromatography on silica gel (n-hexane/ether, 5/1).
Themixturewasstirredmagneticallyuntilcompleteconsumptionofsubstrate.
Dilutehydrochloricacidsolution(15 mL)wasaddedandthemixtureextracted
with chloroform (3Â15 mL). The organic extracts were dried (MgSO4) and
concentrated. The carbonyl compounds were isolated in 61–98% yields.
ACKNOWLEDGMENTS
We are grateful to Razi University Research Council for financial
support of this work.
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Received July 7, 2000