Synthesis of Diaryl Ketones Catalyzed by Al2O 3-ZrO2/S2O82- Solid Superacid

Article abstract of DOI:10.1081/SCC-120027287

The acylation of a variety of aromatic compounds with benzoyl chloride or its derivatives and catalytic amounts of Al₂O₃-ZrO ₂/S₂O₈^2- solid superacid affords the corresponding diaryl ketones in good to excellent yields 75-93% at appropriate temperature.

Full text of DOI:10.1081/SCC-120027287

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Synthesis of Diaryl Ketones Catalyzed by Al2O3‐ZrO2/
S2O8 2- Solid Superacid
Tong‐Shou Jin a , Mi‐Na Yang a , Guo‐Liang Feng a & Tong‐Shuang Li a
a Department of Chemistry, College of Chemistry and Environmental Science, Hebei
University, 88 He Zuo Road, Baoding, 071002, Hebei Province, P. R. China
Version of record first published: 16 Aug 2006.
To cite this article: Tong‐Shou Jin , Mi‐Na Yang , Guo‐Liang Feng & Tong‐Shuang Li (2004): Synthesis of Diaryl Ketones
Catalyzed by Al2O3‐ZrO2/S2O8 2- Solid Superacid, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 34:3, 479-485
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 3, pp. 479–485, 2004
Synthesis of Diaryl Ketones Catalyzed by
Al2O3-ZrO2/S2O282 Solid Superacid
*
Tong-Shou Jin, Mi-Na Yang, Guo-Liang Feng,
and Tong-Shuang Li
Department of Chemistry, College of Chemistry and Environmental
Science, Hebei University, Baoding, Hebei Province, P. R. China
ABSTRACT
The acylation of a variety of aromatic compounds with benzoyl chloride
or its derivatives and catalytic amounts of Al2O3–ZrO2/S2O282 solid
superacid affords the corresponding diaryl ketones in good to excellent
yields 75–93% at appropriate temperature.
Key Words: Acylation; Solid superacid; Catalyzed; Synthesis; Diaryl
ketones.
The synthesis of diaryl ketones with benzoyl chloride or its derivatives
and aromatic compounds is very useful in preparative organic chemistry and
*
Correspondence: Tong-Shou Jin, Department of Chemistry, College of Chemistry and
Environmental Science, Hebei University, 88 He Zuo Road, Baoding 071002, Hebei
Province, P. R. China; E-mail: orgsyn@mail.hbu.edu.cn.
479
DOI: 10.1081/SCC-120027287
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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Jin et al.
the diaryl ketones are also important starting materials for synthesis of valu-
able medicines, pesiticides and perfumes.[1,2] In the conventional methods, the
synthesis of diaryl ketones was carried out by Friedel–Crafts aroylation
reaction. Friedel–Crafts acylation reactions generally require molar amounts
of Lewis acid of particular metallic salts such as AlCl3, BiF3, FeCl3 and
zeolites as catalyst, which form complexes with both the acylation and the
carbonyl product.[1] Work-up, consequently, is needed to decompose these
complexes and the catalyst is usually non-recoverable. Also reported, Iron(III)
Sulphate,[3] methanesulfanic acid,[4] palladium,[5] trimethyl po1yphosphate,[6]
Nafion-H,[7] bismuth(III) trifuloromethanesulfonate,[8] trifluoromethane-
sulfonic acid.[9] bismuth(III) chloride and Triflate,[10] were applied to acceler-
ate this reaction. While each of the above methods has its own merit, these
methods have not been entirely satisfactory, owning to such drawbacks as low
yield, longer reaction time, problems of corrosion, environmental pollution
and the catalysts are not easily obtained, used in excess of molar amounts,
expensive and unrecoverable. There is therefore, substantial interest to cata-
lyze this reaction with solid superacid, which do not form stable complexes
with carbonyl compounds.
Solid superacids have been used as an efficient catalysts for a variety of
organic reaction.[11] Solid acids are better than liquid acids in terms of green
chemistry since they are efficient, non-pollutive, non-corressive and have high
activity. Recently, we have focused on our attention on solid superacid as
catalyst. Herein we wish to report an efficient and practical procedure for the
synthesis of diaryl ketones by Friedel–Crafts reaction of benzoyl chloride or
its derivatives with aromatic compounds catalyzed by Al2O3–ZrO2/S2O822
solid superacid at appropriate temperature in good to excellent yields (Sch. 1).
The results are summarized in Table 1.
The aroylation was carried out with heating a stirred mixture of the
corresponding benzoyl chloride or its derivatives, aromatic compounds and
the Al2O3–ZrO2/S2O282 solid superacid catalyst at appropriate temperature.
Products diaryl ketones were simply isolated by filtering the reaction mixture
and distilling off the solvent. The solid products were purified by recrystal-
lization in the usual way, the liquid products were purified by distillation under
Scheme 1.

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Jin et al.
reduced pressure or by column chromatography on silica gel using hexane/
ethylacetate as eluent.
The benzoylation of toluene on three catalysts Al2O3/S2O282 (yield 12%),
ZrO2/S2O282 (yield 52%) and Al2O3–ZrO2/S2O822 (yield 78%) shows that the
catalytic activity of Al2O3-ZrO2/S2O22 is the best compared with Al2O3/
S2O282 and ZrO2/S2O282 in this kind of reaction. The catalytic activity of
Al2O3–ZrO2/S2O282 increases with Al2O3 content up to 3.0 mol% and then
decreases as the Al2O3 content is further increased. That is to say that the
addition of an appropriate amount of alumina to ZrO2/S2O282 promotes the
catalytic activity of the catalyst for the benzoylation of aromatic compounds
with benzoyl chloride. An interaction of Zr with Al atoms, due to the
formation of a Zr–O–Al bond in the binary oxide enhances the acid strengths
of superacidic sites.[14] Since the electronegativity of Al3þ is Larger than that
of Zr4þ, the partial charge on Zr is increased after the formation of the Zr–O–
Al bond, which may help to stabilize the surface surfur complex and to
increase the number of strong acid sites. The acid strength distribution of the
acid sites on other catalysts and the structure aspects of the Al-promoted
catalysts will be further explored. So we believed that the acid sites with acid
strength in the superacidic range are needed for the formation of the reaction
intermediate and the stronger the acid sites the higher the activity of the
catalyst for the acylation reaction.
The results of experiment had shown that in the absence of catalyst no
product was observed even with prolonged heating. The lowering of reaction
temperature was detrimental to efficiency. For example, entry 9 at 1008C for
6 hours only 35% yield of product was obtained, whereas 85% yield was
obtained at 1508C for 5 hours. The substitution effects have been studied in
these reactions (Table 1). According to the data listed in the Table 1, it is clear
that electron-donating groups have increased the reaction speed as well as
reaction yields and on the other hand, electron-withdrawing groups have
decreased yields and increased reaction time.
The Al2O3–ZrO2/S2O282 catalyst can be readily regenerated in the
following way: the catalyst was filtered off after the reaction, then washed
with acetone and ether successively, and then was dried at 128C for 2 h. The
regenerated catalyst could be reused four times for the synthesis of diphenyl-
ketone without significant loss of activity.
In conclusion, we have developed a practical and efficient method for the
synthesis of aromatic ketones under solvent-free conditions using aromatic
compounds and benzoyl chloride or its derivatives in the presence of Al2O3–
ZrO2/S2O282. It is clear that this method is superior from the view of operation
simplicity, higher yields, short reaction time, non-corrosion. non-pollution.
environment-friendly and employs a reusable catalyst. This methodology will
be better than the reported methods.

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EXPERIMENTAL
Melting points are uncorrected. All the liquid parent materials are fresh
stilled. The products were characterized by comparison of their melting or
boiling points with literature values.
Preparation of Al2O3-ZrO2/S2O282 Solid Superacid
The catalyst Al2O3-ZrO2/S2O282 solid superacid was prepared as
follows. Zr(OH)4 and Al(OH)3 were infused in (NH4)2S2O8 (l mol/L) for 4
hours, the filtered off, drying at 1108C for 2 hours. smash over 150 mesh,
dried calcined in furnace at 6508C for 4 hours and finally stored in a
desiccator until use.
General Procedure for the Synthesis of Diaryl Ketones
A mixture of aromatic compound 1 (0.2 mol), benzoyl chloride 2
(0.04 mol) and Al2O3-ZrO2/S2O282 (1.0 g) was stirred at suitable temperature
for the corresponding time showed in the Table 1. The HCl effluent gas was
absorbed by NaOH solution. The progress of the reaction was monitored with
TLC. After completion of the reaction, the mixture was cooled to room
temperature and the catalyst was filtered off and then washed with the
aromatic compound. The obtained liquid was distilled in vacuo to reclaim the
unreacted father materials, Et2O (15 mL) was added, the organics was washed
with 5% NaHCO3 (15 mL) and brine (2 ꢀ 15 mL) successively and then dried
with MgSO4. Evaporation of the solvent under reduced pressure afforded the
crude product. The crude product was purified by recrystallization with
ethanol or by column chromatography on silica gel using hexane/ethylacetate
(9 : 1) as eluent to afford the pure product 3.
ACKNOWLEDGMENTS
We wish to thank Natural Science Fund of China (29872011), Educa-
tional Ministry of China, Educational Department of Hebei Province (990104)
and Science and Technology Commission of Hebei Province for support of
this work.

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Received in Japan June 2, 2003

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