Indian Journal of Chemistry
Vol. 42B, July 2003, pp. 1765- 1767
Note
Benzimidazolium dichromates : Efficient
reagents for selective oxidation of alcohols
to carbonyl compounds
K Ramaiah, P K Dubey*, J Ramanatham & C Ravi Kumar
Dept. of Chemistry, College of Engg., J. N. T. University,
Kukatpally, Hyderabad, (AP) 500 072, India.
and
J S Grossert
Dept. of Chemistry , Dalhousie University, Halifax , NS,
Canada B3H 4J3 .
Received 19 September 200 I: accepted (revised) 6 January 2003
Benzimidazolium dichromates have been used for the selective
and efficient oxidation of simple alcohols to carbonyl compounds.
2-Methylbenzimidazolium dichromate has been used as a standard
compound. It has been found to oxidize selectively , primary alco-
hols to aldehydes, without any over-oxidation, and secondary
alcohols to ketones. Of the several solvents explored, acetic acid
at RT has been found to be the best medium for ox idation .
The selectivity in the oxidation of primary and secon-
dary alcohols to the corresponding carbonyl com-
pounds has been widely explored with a variety of
special reagentsl. During our attempts to synthesize 2-
acetylbenzimidazole from 2-ethylbenzimidazole by
oxidizing the methylene carbon of the latter, with
cr0 3 in gl.acetic acid, benzimidazolium dichromates
were obtained. The structural elucidation of these
benzimidazolium dichromates were carried out and
communicated by us recentl/. We now wish to report
the sy nthetic utility of these benzimidazolium di-
chromates in the selective oxidation of various pri-
mary and secondary alcohols to the corresponding
aldehydes and ketones respectively in acetic acid me-
dium at RT.
Results and Discussion
In continuation of our work on preparation of 2-
acetylbenzimidazoles, we have found that benzimida-
zoles also form similar dichromate salts as pyridinium
I N
R'
( } 4-CH(OH)-R" +
h N
[e
IH
h
rN
_.1-R1
N
(",0. "
Ad) II
RT
• ~~~CO'R"
H •
I 2 . 4
Scheme I
dichromates.These compounds, have been isolated
2
and characterized earlier by us . In an attempt to
check the selective oxidizing capabilities of these
benzimidazolium dichromates different reactions have
been conducted and cond iti ons optimized.
Initially different so l vents like CH 2Ci 2 , CHCh,
CH 3CN, DMF and AcOH have been tried for the oxi-
dation of PhCH 20H and 1 (R'=H, R"=CH 3), it was
found that acetic acid is the best solvent to harness the
oxidizing potential of these dichromates.
Using gl.acetic acid as solvent, a comparative study
has been made regarding the oxidizing capabilities of
various 2 (R=H, CH 3, C 2H 5 and n-C3H7) obtained in
this work 2 . 2-((-Hydroxyethyl)benzimidazole Ib
(R' =H , R"= CH 3) has been used as the reference
compound and its oxidations with various 2 (R=H,
CH 3, C 2 H 5 and n-C3H7) were evaluated in terms of the
yield and purity of 2-acetylbenzimidazole 3b (R'=H,
R"= CH 3) obtained. The method of processing the
reaction mixtures were similar to that described in the
case of 2b as above. Results of this study are shown
in Table I.
Using the optimized conditions, different primary
and secondary hydroxylic compounds have been oxi-
dized in good yields and characterized as their 2,4-
DNP derivatives. The above results are tabulated in
Table II.
Advantages
The benzimidazolium di chromates used in this
work have certain advantages over existing organo-
chromium oxidizing agents. For example, (a) for
completion ofoxidation it requires only 1: 1 mole of
reagent per mole of the substrate. (b) The
reprocessing of the reaction mixture is also relati ve ly
easy. (c) The reagent oxidizes primary hydroxy
groups selectively to the corresponding aldehydes
groups without any over-oxidation This is supported
by the fact that the TLC and GC analyses of crude
benzaldehyde obtained by oxidation of benzyl alcohol
~N
+ (Y~4-R +
~N
Cr(lll)
 1766 INDIAN 1. CHEM., SEC B,lUL Y 2003

Table I - Oxidation of various alcohols using 2b (i .e., 2, R=CH 3)

SI Alcohol used Product obtained Molar m.p. m.ps of 2,4- mps of authentic 2,4- Rexn. Temp.
No. yield (%) DNP deriv. (0C) DNP deriv. (0C)
l. n-Butanol n-b utana l 91 121-22 120-22 RT

2. n-pentanol n-pentanal 90 106-08 105-07 RT

3. i-pentanol i-pentanal 90 122-24 12 1-22 RT

4. G lycolic ac id G lyoxa lic ac id 89 18 1-83 180-82 RT

5. Cyclo hexanol Cyc lohexa none 86 16 1-63 160-62 RT

6. Benzyl alcohol Benzaldehyde 92 238-40 235-37 RT

3 4
7. la (R'=H , 3a (R ' =H , R" =H ) 67 230-3 1 233-35 RT
R"=H )
8. Ib 3 (R'=H, 3b5 (R'=H, 67 189-91 190-9 1 Intially at 100°C
R"=CH 3 ) R"=CH 3) for 5 min and later at
RT for 0.5 hrs.
9. Ie (R ' =CH 3 , 3e (R ' =CH 3 , 85 190
R" =CH 3) R"=CH 3)
10. Id (R ' =C 2 Hs, 3d (R ' =C 2 Hs, 89
104
R"=CH 3) R"=CH 3 )
II Ie (R ' =CH 2Ph, 3e (R' =CH 2 Ph,
83 106
R"=CH 3) R"=CH 3)

Table 11- Comparative study of oxidizing capabi liti es using different 2

Alcohols used as 2 used as oxid izing Solvent used Reaction Temp Product obtai ned Molar yield
substrate for ox idation agent (%)

I b (R ' =H , R"=CH 3 ) 21'1, (i.e.2, R= H) AcOH Initi ally at 3b (R'=H, 63

100DC for 5 R"=CH 3)
do 2b, (i.e.2, R= CH 3) AcOH do 67
do 2e, (i.e.2, R= C 2 Hs) AcOH min and later at do 65
RT for 0.5 hrs
do 2d, (i.e.2, R= AcOH do 60
nC 3 H7 )

using this method showed the absence of any benzoic
·acid on co mpari son wi th an authen tic sample of
benzoic acid itself. (d) After isolation of the reaction
product, the benzimidazole i. e., 4 can be recovered
back almost quantitatively and can be reused for the
preparation of 2. (e) Acetic acid being an environ-
ment-friendly solvent, the wash sol utions can be
safely drained out without resorting the serious
recovery unlike in the cases when chlorinated solvents
(like CHCh, CH 2Ch etc., are used. (f) Since the
reagents (i.e., 2) are soluble in acetic acid, the need
for the use of a phase-transfer catalyst can be avoided.
Conclusion
2-S ubstituted/un substituted benzimidazolium di -
chromates can be prepared by different routes in the
laboratory using simple procedures. These com-
pounds are stable at RT and can be stored for long
periods of time. 2-Methylbenzimjdazolium dichro-
mate has been used as a sta ndard reagent. It ox idi zes
selecti vely primary alcohol s to aldehydes and secon-
dary alcohols to ketones without any over-oxidation.
Of the several conditions used, acetic acid at RT has
been found to be best suited for oxidation.
Experimental Section
Spectroscopic data were recorded with JASCO Ff-
IR 5300, VARIAN 200 (IH NMR, 200MHz), Hewlet
Packard (EI-MS 70 eV) instruments. Melting points
(mp) were determined in open capillary tubes in sul-
furic acid bath and are uncorrected. TLC analyses
 NOTES
were done on glass plates coated with silica gel-G and
spotting was done using iodine or U V Light.
Preparation of carbonyl compounds using 2b
(General procedure). To a mixture of 2b (2.5
rnmole) in acetic ac id (10 mL) at RT was added a
solution of the ethanol (2 .5 mmole) in acetic acid (5
mL). The mixture was stirred at RT. Complerion of
the reaction was indicated by the suspension getting
cleared and a change in the color of the solution from
yellow/yellowish-orange to green. Thi s usually takes
about 30 min . (for non- volatil e or hi gher boiling
alcohols, the reaction can be monitored by TLC). At
the end of this period, the reaction mixture was
poured into water (75 mL) and the clear ag.solution
extracted with ether (2x30 mL) . The ether ex tract was
washed with water, dried (over anhyd. MgS04 ) and
evaporated to obtain a residue which was the carbonyl
compound. The pH of the ag. solution was adjusted to
- 6 using NaHC03 solution , the separated solid was
filtered, washed with water and dried which was
found to be 4.
Acknowledgement
The authors are deeply indebted to U G C, New
Delhi , for financial support, to J.N.T. University for
laboratory facilities and to Dalhousie University,
Halifax, Canada, for instrumental facilities.
1767
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