Jour nal of the Chi nese Chem i cal So ci ety, 2004, 51, 509-512 509

Sol vent-free Ox i da tion of Alcohols by Silica Sulfuric Acid/Sodium

Dichromate Dihydrate or Potassium Permanganate/Wet SiO2 System

BiBi Fatemeh Mirjalili*a , Mohamad Ali Zolfigol b, Abdolhamid Bamoniri c and Amin Zareia
a
De part ment of Chem is try, Col lege of Sci ence, Yazd Uni ver sity, P. O. Box 89195-741, Yazd, Iran
b
De part ment of Chem is try, Col lege of Sci ence, Bu-Ali Sina Uni ver sity, Hamadan 65174, P. O. Box 4135, Iran
c
De part ment of Chem is try, Col lege of Sci ence, Kashan Uni ver sity, Kashan 51167, Iran

A com bi na tion of sil ica sul fu ric acid and so dium dichromate dihydrate or po tas sium per manganate in the
pres ence of wet SiO 2 was used as an ef fec tive ox i diz ing agent for ox i da tion of al co hols to their cor re sponding
al de hydes or ke tones in sol vent free con di tions.

Keywords: Silicasulfuric acid; Oxidation; Alcohols; Solvent free.

INTRODUCTION ox i da tion of pri mary al co hols to al de hydes by a chro mium

Re cently, some chem ists found that many re ac tions
pro ceed ef fi ciently in the solid state. In deed, in many cases,
solid state or ganic re ac tion oc curs more ef fi ciently and more
se lec tively than does its so lu tion coun ter part. The sol vent
free re ac tion has many ad van tages such as re duced pol lu tion,
low costs, sim plic ity in pro cess, and eas ier work-up. These
fac tors are es pe cially im por tant in in dus try.1
For ox i da tion of or ganic functionalities, one turns of ten
to tran si tion metal cat a lysts,2 high-valent metal ox ides or
their min eral salts. 3 Clas sic re agents of this type are man ga -
nese di ox ide (MnO2 ), po tas sium permangenate (KMnO 4 ),
chro mium tri ox ide (CrO3), po tas sium chromate (K2 CrO4 ),
and po tas sium dichromate (K 2Cr2O 7), 4 and pyridinium chlo -
rochromate. 5 These are all fre quently-used re agents, whether
in the lab o ra tory or in in dus try, and yet they are be set with
mul ti ple li a bil i ties. For sat is fac tory and re pro duc ible re sults,
these ox i dants de mand vig or ous con trol of the ex per i men tal
con di tions. The other draw backs against such ox i dants and
their use in mul ti stage or ganic syn the sis, in spite of their
power, are also their lack of se lec tiv ity, strong protic and
aque ous con di tions, low yields of the prod ucts, and te dious
work-up. For in stance, overoxidation of aldehydes to car box-
ylic acids is often an unavoidable side reaction.
Fur ther more, the el e vated re flux tem per a tures re quired
by some ox i da tion pro ce dures will fa vor in op por tune sec ond-
ary re ac tions. Like wise, the pres ence of strong ac ids or bases,
which are re quired ad juncts as cat a lysts for some re ac tions,
of ten leads to det ri men tal side re ac tions. As an ex am ple, the
(VI) salt in sul fu ric acid is of ten ac com pa nied by for ma tion
of a hemiacetal be tween the re sult ing al de hyde and the al co-
hol sub strate, fol lowed by the ready ox i da tion of this in ter me-
di ate to an es ter.6
RESULTS AND DISCUSSION
We have in tro duced po ten tially use ful ox i dants for se-
lective ox idation and oxidative deprotection of dif ferent
func tional groups. 7 There fore, we de cided to choose a new
re agent or re agent sys tems to over come the above lim i ta-
tions. In ad di tion, for our pur pose both clean and easy work-
up were also im por tant. On the other hand, any re duc tion in
the amount of sul fu ric acid needed and/or any sim pli fi ca tion
in han dling pro ce dures is re quired for risk re duc tion, eco-
nomic ad van tages, and en vi ron men tal pro tec tion.8 In ad di-
tion, there is cur rent re search and gen eral in ter est in sol vent
free sys tems be cause of the im por tance such sys tems have in
in dus try and in de vel op ing tech nol o gies.9 In con tin u a tion of
our stud ies on the ap pli ca tion of in or ganic acidic salts we
found that sil ica sul fu ric acid (I) is an ex cel lent can di date for
acid sul fu ric re place ment in or ganic re ac tions with out any
lim i ta tions such as de struc tion of acid sen si tive func tional
SiO2 OSO3H
I

* Cor re spond ing au thor.E-mail: fmirjalili@yazduni.ac.ir

510 J. Chin. Chem. Soc., Vol. 51, No. 3, 2004 Mirjalili et al.

Table 1. Oxidation of Various Alcohols to Aldehyde and Ketones by Silica Sulfuric Acid (I), Na2Cr2O7.2H2O (II), and Wet Sio2 60%
w/w in Solvent Free Conditions
Entry Substrate Product Substrate Na2Cr2O72H2O Wet SiO2 Silica Sulfuric Condition Time Yielda
(mmole) (mmole) (g) Acid (g) (min) (%)
1 Benzyl alcohol Benzaldehyde 2.9 1 0.35 0.15 r.t 30 95

2 Cyclohexanol Cyclohexanone 4.38 1.85 0.45 0.45 r.t 30 65

3 m-Methoxy m-Methoxy 1.85 0.64 0.35 0.1 r.t 30 90

benzylalcohol benzaldehyde
4 Hydroquinone p-Benzoquinone 1 0.33 0.3 0.05 r.t 30 95
5 Benzhydrol Benzophenone 3 1 1 0.15 r.t with grinding 30 90
6 1-Hexanol Hexanal 3 1 0.25 0.15 r.t 30 70
7 Benzoin Benzil 3 1.3 2 0.2 r.t with grinding 60 30
8 P-Chloro P-Chloro 3 1 0.35 0.15 r.t 30 90
benzylalcohol benzaldehyde
9 2-Pentanol 2-Pentanone 3 1 0.25 0.15 r.t 30 70
10 1-Butanol Butanal 3 1 0.25 0.15 r.t 30 95
11 Mandelic Acid Benzaldehyde 0.75 0.25 0.9 0.037 r.t with grinding 60 40
12 Bezylalcohol Benzaldehyde 0.3 1 0.35 0.15 r.t 30 95b
+ +
Cyclohexanol 0.3 0
a
Isolated yields.
b
Competitive reaction.

Table 2. Oxidation of Various Alcohols to Aldehyde and Ketones by Silica Sulfuric Acid (I), KMnO4 (II), and Wet SiO2 60% w/w
under Solvent Free Conditions
Entry Substrate Product Substrate KMnO4 Wet SiO2 Silica Sulfuric Condition Time Yielda
(mmole) (mmole) (g) Acid (g) (min) (%)
1 Benzyl alcohol Benzaldehyde 2 1 0.35 0.35 r.t 30 90
2 Cyclohexanol Cyclohexanone 2 1 0.24 0.4 r.t 30 70
3 m-Methoxy m-Methoxy 2 1 0.24 0.35 r.t 30 90
benzylalcohol benzaldehyde
4 Hydroquinone p-Benzoquinone 2 1 0.24 0.5 r.t 30 95
5 Benzhydrol Benzophenone 2 1 0.24 1 r.t with grinding 30 90
6 1-Hexanol Hexanal 2 1 0.24 0.4 r.t 30 70
7 Benzoin Benzil 2 1 0.24 1 r.t with grinding 30 30
8 p-Chloro p-Chloro 2 1 0.24 0.35 r.t 30 95
benzylalcohol benzaldehyde
9 2-Pentanol 2-Pentanone 2 1 0.24 0.4 r.t 30 80
10 1-Butanol Butanal 2 1 0.24 0.4 r.t 30 90
11 Mandelic Acid Benzaldehyde 1 0.5 0.14 0.5 r.t with grinding 30 35
12 Bezylalcohol Benzaldehyde 2 1 0.35 0.35 r.t 30 90b
+ +
Cyclohexanol 2 0
a
Isolated yields.
b
Competitive reaction.

groups.1 0 Het er o ge neous re agent sys tems have many ad van- cour aged us to seek a com pletely het er o ge neous sys tem for
tages such as sim ple ex per i men tal pro ce dures, mild re ac tion the ox i da tion of var i ous al co hols. In this ar ti cle we would like
con di tions and minimization of chem i cal wastes as com pared to re port a sim ple and con ve nient method for the ef fec tive
to their liq uid phase coun ter parts. 10-13 The above facts en - con ver sion of al co hols (1) to their cor re spond ing al de hydes
Sol vent-free Ox i da tion Alcohols
or ke tones (2) un der mild and sol vent free con di tions
(Scheme I).
Scheme I
I,II
or
I,III
R1 R2 CHOH R1 R2 C O
Wet SiO2
1 2
In this work, dif fer ent types of al co hols (1) were sub -
jected to ox i da tion re ac tion in the pres ence of sil ica sul fu ric
acid (I), Na 2 Cr 2O 7.2H2 O (II) or KMnO4 (III), and wet SiO2
(60% w/w) with out any sol vent. The ox i da tion re ac tions were
per formed un der mild and sol vent free con di tions with ex cel-
lent yields (Ta bles 1 and 2). It was also ob served that the ox i-
da tion of pri mary al co hols ( 1) gives only aldehyde.
In or der to show the chemoselectivity of the method,
we have car ried out the suc cess ful ox i da tion of benzyl al co-
hol in the pres ence of cyclohexanol (Scheme II and En try 13
in both tables).
Scheme II
H O O
CH2OH OH
SiO2 OSO3 H
+ +
Na 2Cr2 O7
or
KMnO4 90-95% 0%
wet SiO2
In con clu sion, the cheap ness and the avail abil ity of the
re agents, easy and clean work-up, and high yields make this
method at trac tive for large-scale op er a tions. This pro ce dure
is very sim ple and con tam i na tion by over ox i da tion side-
prod ucts is avoided. More over, the new el e ment here is that
the re ac tion is in sol vent free con di tions. This could be worth-
while for over com ing the lim i ta tions of chro mium based ox i-
dants. We be lieve that the pres ent meth od ol ogy would be an
im por tant addition to existing methodologies.
EX PER I MEN TAL SEC TION
General
Chem i cals such as al co hols, so dium dichromate dihy-
drate, po tas sium per manga nate, di chloro methane and sil ica
gel 60 (0.040-0.063 mm, cat. No = 109385, Merck) were pur-
J. Chin. Chem. Soc., Vol. 51, No. 3, 2004 511
chased from Fluka, Merck and Aldrich chem i cal com pa nies.
Sil ica sul fu ric acid was syn the sized ac cord ing to the our pre-
vi ously re ported pro ce dure. 10,11 The ox i da tion prod ucts were
char ac ter ized by com par i son of their spec tra (IR, 1 H NMR),
TLC and phys i cal data with the au then tic sam ples.
Ox i da tion of hydroquinone to p-benzoquinone, a typical
procedure
A mix ture of hydroquinone (0.12 g, 1 mmole), po tas-
sium per manga nate (0.1 g, 0.33 mmole), sil ica sul fu ric acid
(0.05 g) and wet SiO2 (60% w/w, 0.3 g) in a ves sel was shaken
for 30 min utes. Then 10 mL of CH2 Cl2 as sol vent was added
to the ves sel, and the het er o ge neous mix ture was fil tered. The
sol vent was re moved un der re duced pres sure. The solid was
crys tal lized by n-hex ane. The p-benzoquinone was ob tained
in quan ti ta tive yield.
ACKNOWLEDGMENT
Fi nan cial sup port for this work by the re search af fairs
sec tions, Yazd University, Bu-Ali Sina University, and
Kashan Uni ver sity, are grate fully ac knowl edged and also Mr.
F. Fallah and Mr. H. Babazadeh are thanked for their help.
Received July 7, 2003.
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