3,6-bis(triphenylphosphonium) cyclohexene peroxodisulfate as an efficient and mild oxidizing agent for conversion of alkylbenzenes to corresponding carbonyl compounds

Article abstract of DOI:10.1081/SCC-120006010

Oxidation of a series of alkylbenzenes by BTPCP under neutral conditions to corresponding carbonyl compounds is described.

Full text of DOI:10.1081/SCC-120006010

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3,6-BIS(TRIPHENYLPHOSPHONIUM) CYCLOHEXENE
PEROXODISULFATE AS AN EFFICIENT AND
MILD OXIDIZING AGENT FOR CONVERSION OF
ALKYLBENZENES TO CORRESPONDING CARBONYL
COMPOUNDS
Rashid Badri a & Mousa Soleymani a
a Chemistry Department , Chamran University , Ahvaz, Iran
Published online: 16 Aug 2006.
To cite this article: Rashid Badri & Mousa Soleymani (2002) 3,6-BIS(TRIPHENYLPHOSPHONIUM) CYCLOHEXENE
PEROXODISULFATE AS AN EFFICIENT AND MILD OXIDIZING AGENT FOR CONVERSION OF ALKYLBENZENES TO CORRESPONDING
CARBONYL COMPOUNDS, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic
Chemistry, 32:15, 2385-2389, DOI: 10.1081/SCC-120006010
To link to this article: http://dx.doi.org/10.1081/SCC-120006010
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 15, pp. 2385–2389, 2002
3,6-BIS(TRIPHENYLPHOSPHONIUM)
CYCLOHEXENE PEROXODISULFATE
AS AN EFFICIENT AND MILD OXIDIZING
AGENT FOR CONVERSION OF
ALKYLBENZENES TO CORRESPONDING
CARBONYL COMPOUNDS
*
Rashid Badri and Mousa Soleymani
Chemistry Department, Chamran University,
Ahvaz, Iran
ABSTRACT
Oxidation of a series of alkylbenzenes by BTPCP under
neutral conditions to corresponding carbonyl compounds is
described.
Peroxodisulfate radical anion SOꢀ4 ꢁ, is one of the most important and
strong one-electron oxidant in organic synthesis. Its ability to oxidize a
variety of organic compounds has been under intensive investigations in
recent years.[1–7] The conversion of alkylbenzenes to corresponding carbonyl
compounds is important in organic synthesis and many reagents such as:
Ceric amonium nitrate in aqueous acetic acid or in HClO4[8] and along with
potassium bromate,[9] Chromium trioxide in acetic anhydride followed by
*Corresponding author. E-mail: rashibadri@yahoo.com
2385
DOI: 10.1081/SCC-120006010
Copyright & 2002 by Marcel Dekker, Inc.
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2386
BADRI AND SOLEYMANI
hydrolysis,[10] Potassium permanganate absorbed on alumina,[11] Selenium
dioside,[12] Chromyl chloride[13] and Silver(II) oxide in phosphoric acid,[14]
have been used to accomplish such goals. However the above reagents
either were used in aqueous acidic solution or in the presence of a
metal ion as catalyst. Some of the recently developed reagents which involve
the use of peroxodisulfate anion radical such as K2S2O8/Cu2þ [15]
,
(NH4)2S2O8/Cu(OAc)2 and [Ag(Py)4]S2O8,[17] show non or poor selectiv-
[16]
ity towards the presence of some selective functionalities. Recently we have
reported the synthesis and application of 3,6-bis(triphenylphosphonium)
cyclohexene peroxodisulfate (BTPCP) as an efficient and selective oxidant
in nonaqueous medium.[18] We now wish to report a simple, convenient,
mild and selective method for the oxidation of alkylbenzenes to their corres-
ponding carbonyl compounds with BTPCP under neutral conditions and in
the absence of metal catalysts. This method shows to be of considerable
utility for the oxidation of alkylbenzenes at benzylic position. The procedure
developed consists of simply addition of BTPCP in small portions to a
refluxing solution of alkylbenzene in aqueous acetonitrile. The results
obtained are summarized in Table 1.
Results in Table 1 indicate that toluene and its substituted derivatives
carrying both electron-withdrawing and electron-donating groups converted
to corresponding aldehydes in good to excellent yields (Entries 1–10).
Further oxidation of aldehydes to their carboxylic acids was not observed.
The data also demonstrate that the yields obtained from toluenes with
electron-donating groups (Entries 2–4) are to some extent higher than the
yields from substrates with electron-withdrawing groups (Entries 5–10).
With more complex alkyl side chains on the ring and with indane and
flurene (Entries 11–19) the products obtained are corresponding ketones
in moderate to high yields. Methyl pyridine failed to give the corresponding

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OXIDATION OF ALKYLBENZENES BY BTPCP
2387
Table 1. Oxidation of Alkylbenzenes to Carbonyl Compounds by BTPCP
Time
(min)
Yield
(%)a
Entry
Substrate
Product
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
PhCH3
PhCHO
22
25
25
25
25
25
30
45
45
45
25
25
30
30
30
25
25
91
93
95
92
88
86
83
55
57
59
91
84
56
79
70
74
81
p-MeC6H4CH3
p-OMeC6H4CH3
o-OMeC6H4CH3
p-ClC6H4CH3
o-ClC6H4CH3
p-BrC6H4CH3
p-NO2C6H4CH3
m-NO2C6H4CH3
o-NO2C6H4CH3
PhCH2CH3
p-MeC6H4CHO
p-OMeC6H4CHO
o-OMeC6H4CHO
p-ClC6H4CHO
o-ClC6H4CHO
p-BrC6H4CHO
p-NO2C6H4CHO
m-NO2C6H4CHO
o-NO2C6H4CHO
PhCOCH3
PhCH2CH2Br
PhCOCH2Br
PhCH2CH2CH2OH
Ph(CH2)3CO2Et
PhCH2CH¼CHCO2Et
o-OHC6H4CH2CH¼CH2
PhCH2Ph
PhCOCH2CH2OH
PhCO(CH2)2CO2Et
PhCOCH¼CHCO2Et
o-OHC6H4COCH¼CH2
PhCOPh
18
19
20
25
25
45
65
70
–
aYields refer to isolated products. Products were characterized by comparison of
1
their physical data, IR and H NMR spectra with those of known samples.
aldehyde. Chemoselectivity of oxidant is shown by Entries 13, 15 and 16 in
which some selective functionalities such as carbon–carbon double bond
and hydroxy groups remained intact. It is noteworthy that the same pro-
cedures were carried out in other solvents such as: CH2Cl2, CHCl3, THF,
Et2O, hexane and C6H6, but only with aqueous acetonitrile the reactions
were clean and afforded high yields.
In conclusion, neutral and mild reaction conditions, absence of a
metal ion catalyst, high chemoselectivity of the oxidant, easy work-up

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2388
BADRI AND SOLEYMANI
and good to excellent yields of desired products are advantages of this
method.
GENERAL PROCEDURE FOR THE
OXIDATION OF ALKYLBENZENES
To a solution of substrate (1 mmol) in CH3CN/H2O (5/1, 10 mL) in a 50 mL
round-bottomed flask equipped with a condencer and a magnetic stirrer and
under reflux condition was added 3,6-bis(triphenylphosphonium) cyclo-
hexene peroxodisulfate (2 mmol) in small portions over (22–45) min. The
progress of the reaction was monitored by TLC (eluent; CCl4/CH3CO2Et:
6/1). After completion of the reaction, the mixture was filtered and the
solvent was evaporated. The resulted crude material was purified on a
silica-gel plate with appropriate solvent. Pure carbonyl compounds were
obtained in 55–95% yields (Table 1).
ACKNOWLEDGMENT
We thank Chamran University for financial support of this work.
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OXIDATION OF ALKYLBENZENES BY BTPCP
2389
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Received in Japan May 21, 2001

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