Ultrasound-promoted synthesis of 1,5-diarylpenta-2,4-dien-1-ones catalyzed by activated barium hydroxide

Article abstract of DOI:10.1080/00397910902883686

1,5-Diarylpenta-2,4-dien-1-ones were synthesized with ultrasound irradiation in the presence of activated barium hydroxide as catalyst. Compared to conventional methods, the present methodology offers several advantages such as excellent yields, simple procedure, short reaction times, and milder conditions.

Full text of DOI:10.1080/00397910902883686

This article was downloaded by: [Southern Illinois University]
On: 19 December 2014, At: 08:40
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Synthetic Communications: An
International Journal for Rapid
Communication of Synthetic
Organic Chemistry
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
Ultrasound-Promoted Synthesis
of 1,5-Diarylpenta-2,4-dien-1-
ones Catalyzed by Activated
Barium Hydroxide
Ying Xin a , Zhi-He Zang a & Feng-Lei Chen a
a Pharmaceutical College, Chengdu Medical College ,
Chengdu, China
Published online: 16 Oct 2009.
To cite this article: Ying Xin , Zhi-He Zang & Feng-Lei Chen (2009) Ultrasound-
Promoted Synthesis of 1,5-Diarylpenta-2,4-dien-1-ones Catalyzed by Activated
Barium Hydroxide, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 39:22, 4062-4068, DOI:
10.1080/00397910902883686
To link to this article: http://dx.doi.org/10.1080/00397910902883686
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.
However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness,
or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the
Content should not be relied upon and should be independently verified with

primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions

Synthetic Communications1, 39: 4062–4068, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910902883686
Ultrasound-Promoted Synthesis of
1,5-Diarylpenta-2,4-dien-1-ones Catalyzed
by Activated Barium Hydroxide
Ying Xin, Zhi-He Zang, and Feng-Lei Chen
Pharmaceutical College, Chengdu Medical College, Chengdu, China
Abstract: 1,5-Diarylpenta-2,4-dien-1-ones were synthesized with ultrasound
irradiation in the presence of activated barium hydroxide as catalyst. Compared
to conventional methods, the present methodology offers several advantages such
as excellent yields, simple procedure, short reaction times, and milder conditions.
Keywords: Activated barium hydroxide, 1,5-diarylpenta-2,4-dien-1-ones, synthesis,
ultrasound
INTRODUCTION
1,5-Diarylpenta-2,4-dien-1-ones are important intermediates and raw
materials widely used as precursors to drugs,[1,2] nonlinear optical
materials,[3] and so on. They also exhibited considerable biological
activities.[4–8] Traditional synthesis of 1,5-diarylpenta-2,4-dien-1-ones is
usually completed via Claisen–Schmidt condensation between various
substituted acetophenones and cinnamaldehyde using NaOH as a basic
catalyst with a longer reaction time (20 h) and poor product yields
(55–81%).[9] More recently, there are some new catalysts, such as
diphenyltitanocene,[10] Yb(OPf)3,[11] zirconium tetrachloride,[12] and
palladium=TMSCl,[13] to obtain 1,5-diarylpenta-2,4-dien-1-ones. However,
despite the potential utility of these catalysts, many of these methodologies
for the synthesis of 1,5-diarylpenta-2,4-dien-1-ones are associated with
Received November 25, 2008.
Address correspondence to Ying Xin, Pharmaceutical College, Chengdu
Medical College, Chengdu, China. E-mail: tibet99@tom.com
4062

Synthesis of 1,5-Diarylpenta-2,4-dien-1-ones
4063
Scheme 1. Synthesis of 1,5-diarylpenta-2,4-dien-1-ones.
several shortcomings such as long reaction time, the cost of expensive
catalyst, or difficult experimental operation. Thus, the development of
a simple, highly effcient methodology for synthesis of 1,5-diarylpenta-
2,4-dien-1-ones remains desired.
Ultrasound has increasingly been used in organic synthesis in the
past three decades.[14–16] A large number of organic reactions can be
carried out in greater yields, shorter reaction time, and milder conditions
under ultrasound irradiation.[17–26] For example, Jin et al.[27] reported
that Claisen–Schmidt condensation of various substituted acetophenones
with cinnamaldehyde catalyzed by KF–Al2O3 gave (2E,4E)-1,5-
diarylpenta-2,4-dien-1-ones in 67–92% yields in 5–60 min under
ultrasound irradiation. Activated barium hydroxide have been used as
catalysts in organic synthesis because these compounds are relatively
nontoxic, easy to handle, low cost, and high catalytic activity.[28–30] For
instance, in 1984, Sinisterra and Garcia-Raso[28] reported that Claisen–
Schmidt condensation of acetophenone with benzaldehyde catalyzed by
activated barium hydroxide gave 98% of (2E)-1,3-diphenylprop-2-
en-1-one under refluence condition in 1 h. Later, Fuentes et al.[30]
reported that synthesis of (2E)-1,3-diarylprop-2-en-1-ones using activated
barium hydroxide was completed at room temperature within 10 min in
36–79% yields under ultrasound.
All of these results prompted us to study a simple, highly effcient
methodology for synthesis of the Claisen–Schmidt condensation of
various substituted acetophenones with cinnamaldehyde catalyzed by
activated barium hydroxide under ultrasound irradiation. Here, we
report for the first time a facile and effcient protocol for the synthesis
of 1,5-diarylpenta-2,4-dien-1-ones in the presence of a catalytic amount
of activated barium hydroxide under ultrasonication (Scheme 1).
RESULTS AND CONCLUSIONS
As shown in Table 1 and Scheme 1, 1,5-diarylpenta-2,4-dien-1-ones (3a–j)
were synthesized in better yields for the condensation of various
substituted acetophenones (1) with cinnamaldehyde (2), which were

4064
Y. Xin, Z.-H. Zang, and F.-L. Chen
Table 1. Synthesis of 1,5-diarylpenta-2,4-dien-1-ones by activated barium
hydroxide under ultrasound irradiation
Entry
a
Ar1
C6H5
Ar2 t (min) Yield (%)a
Mp. (ꢀC) (lit.)
Reference
27
C6H5
40
300
300
35
270
30
240
30
270
70
420
20
180
35
300
40
360
40
85
102–103 (102.7–103)
67b
0c
b
c
d
e
f
4-FC6H5
4-ClC6H5
4-BrC6H5
C6H5
C6H5
C6H5
82
85–86 (85.2–86.3)
141–142 (141.3–142.8)
145–146 (146.2–147.3)
85–86 (85.7–85.9)
172–173 (172.3–173.5)
178–179 (178.9–179.1)
111–112 (112–113)
81–82 (82)
27
27
27
27
27
27
31
31
31
87b
88
82b
90
84b
78
4-CH3OC6H5 C6H5
4-NO2C6H5 C6H5
64b
92
86b
83
g
h
i
2,4-Cl2
2-Furyl
2-Furyl
C6H5
C6H5
80b
77
C6H5
76b
73
2-Furyl
2-Furyl
300
45
70b
80
j
60–61 (61)
300
74b
aIsolated yield based on cinnamaldehyde.
bStirred with activated barium hydroxide without ultrasound.
cStirred without activated barium hydroxide without ultrasound.
catalyzed by activated barium hydroxide under ultrasound irradiation at
room temperature within 20–70 min. In the absence of ultrasound, the
time of the condensation reaction was within 180–420 min. For example,
the mixture of acetophenone (1a), cinnamaldehyde, and activated barium
hydroxide was stirred at room temperature for 300 min to produce
1,5-diphenylpenta-2,4-dien-1-one in 67% yield. The reaction was carried
out in 85% yield at room temperature for 40 min under ultrasonication.
Therefore, with treatment of ultrasonication, results show that the yields
of condensation reaction are similar or even more than those without such
treatments as described in Table 1, as well as having short reaction times.
Catalyst-activated barium hydroxide is imperative for the con-
densation reaction. For example, the condensation of acetophenone
(1a) with cinnamaldehyde under ultrasound was studied. In the
absence of activated barium hydroxide, the condensation did not

Synthesis of 1,5-Diarylpenta-2,4-dien-1-ones
4065
take place at room temperature. Therefore, we must say that the
active sites of the catalyst are activated by ultrasound, favoring their
catalytic activity.
In conclusion, synthesis of 1,5-diarylpenta-2,4-dien-1-ones was
carried out for the condensation between various substituted acetophe-
nones with cinnamaldehyde catalyzed by activated barium hydroxide
under ultrasound. The present procedure was carried out in a shorter
reaction time with easier operation and greater yield.
EXPERIMENTAL
Liquid acetophenones and cinnamaldehyde were purified by distillation
1
prior to use. Melting points were uncorrected. H NMR spectra were
measured on a Bruker (400 MHz) spectrometer using tetramethylsilane
(TMS) as internal standard and CDCl3 as solvent. Sonication was per-
formed in a KQ-100E ultrasonic cleaner with a frequency of 40 kHz
and a nominal power 100 W. The reaction flask was placed with the
maximum energy area in the cleaner, and the reaction temperature was
controlled by a water bath.
Preparation of the Catalyst (Activated Barium Hydroxide)[32]
The barium hydroxide catalyst was prepared by heating commercial
barium hydroxide octahydrate at 200ꢀC for 3 h. The catalyst was stored
in a desiccator over sodium hydroxide pellets.
General Experimental Procedure for the Preparation
of 1,5-Diarylpenta-2,4-dien-1-ones (3)
Substituted acetophenones (1, 2.0 mmol), cinnamaldehyde (2,
2.0 mmol), absolute ethanol (5 ml), and activated barium hydroxide
(0.30 g) were added in a Pyrex flask (25 ml). The mixture was irra-
diated in the water bath of an ultrasonic cleaner at room temperature
for the period as indicated in Table 1. [Sonication was continued until
cinnamaldehyde disappeared as indicated by thin-layer chromato-
graphy (TLC).] Then the mixture was dissolved in diethyl ether. The
catalyst was removed by filtration and washed with diethyl ether.
The solvent was evaporated under reduced pressure, and the residue
was crystallized with absolute ethanol to give 1,5-diarylpenta-2,4-
dien-1-ones.

4066
Y. Xin, Z.-H. Zang, and F.-L. Chen
The authenticity of the products was established by comparing their
melting points with the literature as well as the spectra data of 1H NMR.
Data
1-(2-Furanyl)-5-phenylpenta-2,4-dien-1-one (3h)
Pale yellow needles; dH (400 MHz): 6.58–6.59 (1H, m), 6.99 (1H, d,
J ¼ 15.6 Hz), 7.02 (2H, d, J ¼ 2.8 Hz), 7.27 (1H, d, J ¼ 3.6 Hz),
7.32–7.40 (3H, m), 7.50 (2H, d, J ¼ 8.0 Hz), 7.65 (1H, s), 7.66–7.70 (1H,
m) ppm.
1,5-Di(2-furanyl)penta-2,4-dien-1-one (3i)
Yellow slice; dH (400 MHz): 6.46 (1H, d, J ¼ 1.6 Hz), 6.50 (1H, d,
J ¼ 3.2 Hz), 6.57–6.58 (1H, m), 6.78 (1H, d, J ¼ 15.2 Hz), 6.87–6.94
(1H, m), 6.98 (1H, d, J ¼ 14.8 Hz), 7.25 (1H, d, J ¼ 4.0 Hz), 7.46 (1H,
s), 7.56–7.60 (1H, m), 7.63 (1H, s) ppm.
5-(2-Furanyl)-1-phenylpenta-2,4-dien-1-one (3j)
Pale yellow slice; dH (400 MHz): 6.46–6.50 (2H, m), 6.78 (1H, d,
J ¼ 15.2 Hz), 6.90–6.96 (1H, m), 7.08 (1H, d, J ¼ 14.8 Hz), 7.47–7.58
(5H, m), 7.97 (2H, J ¼ 8.0 Hz) ppm.
ACKNOWLEDGMENTS
We gratefully acknowledge Wen Chen from China Petro Southwest Oil
and Gas Field Branch Company.
REFERENCES
´
1. Levai, A. Oxazepines and thiazepines, 41: Synthesis of 4-aryl-2,3-dihydro-2-
styryl-1,5-benzothiazepines by the reaction of (E,E)-cinnamylideneacetophenones
with 2-aminothiophenol and their conversion into 2,2-disubstituted 3-acetyl-2,
3-dihydrobenzothiazoles. J. Heterocycl. Chem. 2004, 41, 399–403.
}
´
2. Levai, A.; Jeko, J. Synthesis of 1-substituted 5-aryl-3-styryl-2-pyrazolines
and 3-aryl-5-styryl-2-pyrazolines by the reaction of dibenzylideneacetones
and E,E-cinnamylideneacetophenones with hydrazines. J. Heterocycl. Chem.
2006, 43, 1303–1309.

Synthesis of 1,5-Diarylpenta-2,4-dien-1-ones
4067
3. Wu, D.; Zhao, B.; Zhou, Z. H. An ab initio study on the polarizabilities of
1,5-diphenylpenta-2,4-dien-1-ones. J. Mol. Struct. Theochem. 2004, 682,
83–88.
4. Laliberte, R.; Campbell, D. J.; Bruderlein, F. Anthelmintic activities of
chalcones and related compounds. Can. J. Pharm. Sci. 1967, 2, 37–43.
5. Bardia, R.; Rao, J. T. Synthesis and antimicrobial activity of some a,b-
unsaturated aromatic ketones. Asian J. Chem. 2004, 16, 1194–1196.
6. Yayli, N.; Sivrikaya, S. O.; Yasar, A.; Uecuencue, O.; Guelec, C.; Kolayli, S.;
Kuecuek, M.; Celik, E. Intramolecular 4p photocyclization of chalconoid-like
compounds in solution and antimicrobial activities. J. Photochem. Photobiol.
A 2005, 175, 22–28.
7. Santos, L.; Pedrosa, R. C.; Correa, R.; Cechinel Filho, V.; Nunes, R. J.;
Yunes, R. A. Biological evaluation of chalcones and analogues as hypolipi-
demic agents. Arch. Pharm. 2006, 339, 541–546.
8. Batovska, D.; Parushev, S.; Slavova, A.; Bankova, V.; Tsvetkova, I.; Ninova,
M.; Najdenski, H. Study on the substituents’ effects of a series of synthetic
chalcones against the yeast Candida albicans. Eur. J. Med. Chem. 2007, 42,
87–92.
9. Pinto, D. C. G. A.; Silva, A. M. S.; Levai, A.; Cavaleiro, J. A. S.; Patonay, T.;
Elguero, J. Synthesis of 3-benzoyl-4-styryl-2-pyrazolines and their oxidation
to the corresponding pyrazoles. Eur. J. Org. Chem. 2000, 14, 2593–2599.
10. Nakano, T.; Motegi, Y.; Nagai, Y. Diphenyltitanocene-catalyzed aldol
condensation. Chem. Express. 1993, 8, 297–300.
11. Yi, W. B.; Cai, C. Aldol condensations of aldehydes and ketones catalyzed by
rare earth(III) perfluorooctane sulfonates in fluorous solvents. J. Fluorine
Chem. 2005, 126, 1553–1558.
12. Bora, U.; Saikia, A.; Boruah, R. C. A new protocol for synthesis of
a,b-unsaturated ketones using zirconium tetrachloride under microwave irra-
diation. Indian J. Chem., Sect. B 2005, 44B, 2523–2526.
13. Zhu, Y. L.; Pan, Y. J. A new Lewis acid system palladium=TMSCl for cata-
lytic aldol condensation of aldehydes with ketones. Chem. Lett. 2004, 33,
668–669.
14. Jadidi, K.; Gharemanzadeh, R.; Mehrdad, M.; Darabi, H. R.; Khavasi, H.
R.; Asgari, D. A facile synthesis of novel pyrrolizidines under classical and
ultrasonic conditions. Ultrason. Sonochem. 2008, 15, 124–128.
15. Nandurkar, N. S.; Bhanushali, M. J.; Jagtap, S. R.; Bhanage, B. M.
Ultrasound-promoted regioselective nitration of phenols using dilute nitric
acid in the presence of phase transfer catalyst. Ultrason. Sonochem. 2007,
14, 41–45.
16. Patil, S. B.; Singh, P. R.; Surpur, M. P.; Samant, S. D. Ultrasound-promoted
synthesis of 1-amidoalkyl-2-naphthols via a three-component condensation
of 2-naphthol, ureas=amides, and aldehydes, catalyzed by sulfamic acid under
ambient conditions. Ultrason. Sonochem. 2007, 14, 515–518.
17. Li, J. T.; Yang, W. Z.; Chen, G. F.; Li, T. S. A facile synthesis of a,a0-bis
(substituted benzylidene) cycloalkanones catalyzed by KF=Al2O3 under
ultrasound irradiation. Synth. Commun. 2003, 33, 2619–2625.

4068
Y. Xin, Z.-H. Zang, and F.-L. Chen
18. Li, J. T.; Xu, W. Z.; Yang, L. C.; Li, T. S. One-pot synthesis of 2-amino-
4-aryl-3-carbalkoxy-7,7-dimethyl-5,6,7,8-tetrahydrobenzo[b]pyran derivatives
catalyzed by KF=basic Al2O3 under ultrasound irradiation. Synth. Commun.
2004, 34, 4565–4571.
19. Li, J. T.; Lin, Z. P.; Qi, N.; Li, T. S. Pinacol coupling of aromatic aldehydes
and ketones using TiCl3-Al-EtOH under ultrasound irradiation. Synth. Com-
mun. 2004, 34, 4339–4348.
20. Yang, J. H.; Li, J. T.; Zhao, J. L.; Li, T. S. Pinacol coupling reaction of aro-
matic aldehydes mediated by Zn in acid aqueous media under ultrasound
irradiation. Synth. Commun. 2004, 34, 993–1000.
21. Li, J. T.; Lin, Z. P.; Han, J. F.; Li, T. S. One-pot synthesis of 4-oxo-2-thiox-
ohexahydropyrimidines catalyzed by potassium carbonate under ultrasound.
Synth. Commun. 2004, 34, 2623–2631.
22. Wang, S. F.; Wang, S. B.; Xu, Y. S. Efficient synthesis of trimethylsilyl
pseudohalides catalyzed by PEG400=ZnI2 under ultrasound irradiation.
Synth. Commun. 2005, 35, 1271–1276.
23. Wang, J. S.; Li, J. T.; Lin, Z. P.; Li, T. S. Magnesium-induced pinacol
coupling of aromatic aldehydes and ketones under ultrasound irradiation.
Synth. Commun. 2005, 35, 1419–1424.
24. Wang, S. X.; Wang, K.; Li, J. T. Pinacol coupling reaction of aromatic
aldehydes mediated by aqueous vanadium(II) solution under ultrasound irra-
diation. Synth. Commun. 2005, 35, 2387–2394.
25. Patil, S. B.; Bhat, R. P.; Raje, V. P.; Samant, S. D. Ultrasound-assisted
Pechmann condensation of phenols with b-ketoesters to form coumarins, in
the presence of bismuth(III) chloride catalyst. Synth. Commun. 2006, 36,
525–531.
26. Jagtap, S. R.; Bhanushali, M. J.; Nandurkar, N. S.; Bhanage, B. M.
Ultrasound-assisted synthesis of b-enaminonitriles in the presence of base.
Synth. Commun. 2007, 37, 2253–2258.
27. Jin, H.; Xiang, L. Y.; Wen, F.; Tao, K.; Liu, Q.; Hou, T. P. Improved synth-
esis of chalconoid-like compounds under ultrasound irradiation. Ultrason.
Sonchem. 2008, 15, 681–683.
28. Sinisterra, J. V.; Garcia-Raso, A. An improved procedure for the Claisen–
Schmidt reaction. Synthesis 1984, 502–504.
29. Aguilera, A.; Alcantara, A. R.; Marinas, J. M.; Sinisterra, J. V. Ba(OH)2 as
the catalyst in organic reactions, part XIV: Mechanism of Claisen–Schmidt
condensation in solid–liquid conditions. Can. J. Chem. 1987, 65, 1165–1171.
30. Fuentes, A.; Marinas, J. M.; Sinisterra, J. V. Catalyzed synthesis of chalcones
under interfacial solid–liquid conditions with ultrasound. Tetrahedron Lett.
1987, 28, 4541–4544.
31. Lavrushin, V. F.; Tsukerman, S. V.; Artemenko, A. I. Synthesis of unsatu-
rated ketones containing the furan nucleus. Zh. Obshch. Khim. 1961, 31,
3037–3040.
32. Garcia-Raso, A.; Garcia-Raso, J.; Campaner, B.; Mestres, R.; Sinisterra, J.
V. An improved procedure for the Michael reaction of chalcones. Synthesis
1982, 1037–1041.