HY Zeolite as an extremely active and reusable catalyst in acylation of alcohols with acid anhydride in a solventless system

Article abstract of DOI:10.1080/10426500214120

HY Zeolite is a practical and useful catalyst for acylation of various alcohols and phenols.

Full text of DOI:10.1080/10426500214120

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Phosphorus, Sulfur, and Silicon and the Related
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HY Zeolite as an Extremely Active and Reusable
Catalyst in Acylation of Alcohols with Acid Anhydride in
a Solventless System
M. M. Heravi a b , M. Bolourtchian a , L. Nakhshab a & R. Zadmard a
a Chemistry and Chemical Engineering Research Center of Iran , Tehran, Iran
b Department of Chemistry, School of Sciences , Azzahra University , Vanak, Tehran, Iran
Published online: 27 Oct 2010.
To cite this article: M. M. Heravi , M. Bolourtchian , L. Nakhshab & R. Zadmard (2002) HY Zeolite as an Extremely Active and
Reusable Catalyst in Acylation of Alcohols with Acid Anhydride in a Solventless System, Phosphorus, Sulfur, and Silicon and the
Related Elements, 177:10, 2295-2297, DOI: 10.1080/10426500214120
To link to this article: http://dx.doi.org/10.1080/10426500214120
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Phosphorus, Sulfur and Silicon, 2002, Vol. 177:2295–2297
C
Copyright 2002 Taylor & Francis
1042-6507/02 $12.00 + .00
DOI: 10.1080/10426500290106031
HY ZEOLITE AS AN EXTREMELY ACTIVE
AND REUSABLE CATALYST IN ACYLATION
OF ALCOHOLS WITH ACID ANHYDRIDE
IN A SOLVENTLESS SYSTEM
M. M. Heravi,a,b M. Bolourtchian,a L. Nakhshab,a
and R. Zadmarda
Chemistry and Chemical Engineering Research Center of Iran,
Tehran, Irana and Department of Chemistry, School of Sciences,
Azzahra University, Vanak, Tehran, Iranb
(Received October 17, 2001; accepted December 4, 2001)
HY Zeolite is a practical and useful catalyst for acylation of various
alcohols and phenols.
Keywords: Acylation of alcohols; HY zeolite as catalysts
The acylation of alcohols by acid anhydrides or acyl chlorides is rou-
tinely carried out in the presence of tertiary amines such as triethy-
lamine or pyridine.1,2 Dimethyl amino propylamine is particularly note-
worthy as an efficient catalyst for the acylation of tertiary alcohols.3,4,5
Recently Vedejs and coworkers3,4,6 reported tributylphosphine to be a
similar catalyst for the acylation of alcohols. In addition to the cata-
lysts mentioned above protonic acids such as toluene p-sulphonic acid7
and Lewis acids such as zinc chloride,8 cobalt chloride,9 scandium
trifluoromethane-sulfonate,10 montmorillonite K-10 and KSF11 are also
known to catalyze the acylation of alcohols and phenols. However, none
of the above mentioned catalysts is claimed to work in a solventless
system and to be reusable.
Research was supported by the National Research Council of Iran (NRIC) as a
National Research project, grant number 3709.
After preparation of this article, similar acetylation of alcohols using HSZ-360 zeolite
was reported in R. Bollini, G. Bosica, S. Carloni, Tetrahedron Letters, volume 39, page
6049 (1998).
Address correspondence to M. M. Heravi, Department of Chemistry, School of
Sciences, Azzahra University, Vanak, Tehran, Iran. E-mail: mmheravi@azzahra.ac.ir
2295

2296
M. M. Heravi et al.
TABLE I Actylation of Alcohols, Phenol, and Naphthol with Acetic
Anhydride Catalyzed with H-Y Zeolite
Entry
Substrate
T/ C Time (hr) Ratioa
Product
Yield (%)
1
2
3
4
5
6
7
8
Cinnamylalcohol rt
2
1
2
3
2.5
2
2
2:1
2:1
2:1
2:1
2:1
2:1
4:1
2:1
Cinnamyl acetate
Octyl acetate
Cyclohexyl acetate
Phenyl acetate
Naphthyl acetate
Menthyl acetate
Ethane-1,2,dioldi-acetate
Benzyl acetate
85
92
92
98
81
89
100
68
1-octanol
Cyclohexanol
Phenol
rt
rt
rt
-naphthol
rt
Menthol
Ethylene glycol
Benzyl alcohol
60
60
rt
1
aAcetic anhydride: Substrate (mmol:mmol).
Zeolites as catalysts have received considerable attention in recent
years because of their characteristic properties such as selectivity,
acidity, and thermal stability.12 Their catalytic potential in petrochem-
istry and in oil processing is well documented,13,14 however their appli-
cation in general organic synthesis has not been fully explored. Recently
we have reported the regioselective alkylation of heterocycles using H-Y
zeolite.15 In this article we report that H-Y zeolite serves as an excellent
catalyst for acylation of alcohols and phenols in solvent-free conditions.
As shown in Table I a series of alcohols and phenols were acylated
with acetic anhydride. Primary and secondary alcohols and phenols can
be easily acylated at room temperature. The reaction is clean and the
work up procedure is exceedingly simple involving only the filtration of
zeolite and removal of solvent to obtain the product in high yield and
state of purity.
We next turned our attention towards the possible recycling of the
catalyst with the model substrate 1. The catalyst was filtered on a buck-
ner funnel, washed with acetone, dried in air and reactivated by heating
it at 500 C. Unexpectedly, after allowing the reaction mixture to stir for
1 h at 25 C, product 2 was obtained in a quantitative yield. Moreover
we recycled the zeolite for further five experiments recovering the prod-
uct 2, with similar high yield. This result indicates that H-Y zeolite is
activated after the first cycle and can be therefore reused several times
without losing activity.
In conclusion the present note provides a novel, solvent free and
general method for acylation of alcohols and phenols in the presence of
H-Y zeolite as a reusable catalyst.
(CH3CO)2O
PhCH CH CH2OH
→ PhCH CHCH2OCOCH3
HY-Zeolite
1
2

Acylation of Alcohols
2297
EXPERIMENTAL
All acylated compounds are known and their physical data were
compared with those of authentic samples. Yields refer to GC analysis.
Acylation of Alcohols and Phenols with Acetic Anhydride
Catalyzed by H-Y Zeolite: A Typical Procedure
In a (50 ml) round bottomed flask equipped with a condenser and a
magnetic stirrers a mixture of cinnamyl alcohol (67 mg; 5 mmol), H-Y
zeolite (200 mg), and acetic anhydride (1.02 g, 10 mmol) was stirred at
room temperature for 2 h. The catalyst was removed by filtration and
washed with dichloromethane; the combined liquids were evaporated
under reduced pressure to afford the pure product.
Thus a mixture of acetic anhydride and neat alcohols or phenols
were mixed with the catalytic amounts of H-Y zeolite to afford the
corresponding acyl derivatives. In the absence of H-Y zeolite the re-
actions are sluggish and considerable amounts of starting alcohols are
recovered.
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