Michael addition catalyzed by potassium hydroxide under ultrasound

Article abstract of DOI:10.1081/SCC-120015762

Michael addition of chalcone with active methylene compound such as diethyl malonate, nitromethane and ethyl acetoacetate catalyzed by potassium hydroxide in anhydrous ethanol results Michael adducts in 75-98% yield under ultrasound irradiation in 25-90 m

Full text of DOI:10.1081/SCC-120015762

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Michael Addition Catalyzed by Potassium Hydroxide
Under Ultrasound
a
a
a
a
a
Ji-Tai Li , Yong Cui , Guo-Feng Chen , Zhao-Li Cheng & Tong-Shuang Li
a
College of Chemistry and Environmental Science, Hebei University, Baoding, P.R. China
Published online: 17 Aug 2006.
To cite this article: Ji-Tai Li , Yong Cui , Guo-Feng Chen , Zhao-Li Cheng & Tong-Shuang Li (2003) Michael Addition Catalyzed
by Potassium Hydroxide Under Ultrasound, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 33:3, 353-359, DOI: 10.1081/SCC-120015762
To link to this article: http://dx.doi.org/10.1081/SCC-120015762
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Õ
SYNTHETIC COMMUNICATIONS
Vol. 33, No. 3, pp. 353–359, 2003
Michael Addition Catalyzed by Potassium
Hydroxide Under Ultrasound
Ji-Tai Li,* Yong Cui, Guo-Feng Chen, Zhao-Li Cheng,
and Tong-Shuang Li
College of Chemistry and Environmental Science,
Hebei University, Baoding, P.R. China
ABSTRACT
Michael addition of chalcone with active methylene compound such
asdiethyl malonate, nitromethane and ethyl acetoacetate catalyzed
by potassium hydroxide in anhydrous ethanol results Michael
adductsin 75–98% yield under ultra so und irradiation in 25–90 min.
Key Words: Michael addition; Chalcone; Ultrasound irradiation.
*Correspondence: Ji-Tai Li, College of Chemistry and Environmental Science,
Hebei University, Baoding 071002, P.R. China; E-mail: orgsyn@mail.hbu.edu.cn.
3
53
DOI: 10.1081/SCC-120015762
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
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Li et al.
Michael addition reaction of appropriate carboanionic reagentsto
a,b-unsaturated carbonyl compounds is of great synthetic interest for C-
C bond formation. The versatile Michael reactions have numerous
[1]
applicationsto remote functionalization in the y sn th ei ss of fine
chemicals.
[2]
Michael reaction is classically catalyzed by bases or suitable combi-
nation of aminesand carboxylic or Lewisacidsunder homogeneous
[
3]
[4]
conditions. Some catalysis such as Ba(OH) , KF/Al O , metal (Zn,
2
2
3
[
Co, Ni etc.)(II) complexes, Mg-Al-O-t-Bu hydrotalcite, and phase-
5]
[6]
[7]
transfer catalysis have been reported to be effective to the Michael
reactions, and good results were obtained. However, there were some
disadvantages due to long reaction time or difficult work-up or low yield.
Ultrasound has increasingly been used in organic synthesis in last
[8]
three decades. Compared with traditional methods, this method is
more convenient and easily controlled. A large number of organic reac-
tionscan be carried out in a higher yield, sh orter reaction time or milder
conditionsunder ultra os nic irradiation. And it had been reported that
ultrasound could facilitate Michael reactions in the presence of phase
[
9]
transfer catalyst in heterogeneous system. All of the results stated
above prompt us to study the possibility of Michael addition of chalcone
with active compound such as diethyl malonate, nitromethane and ethyl
acetoacetate under ultrasonitation. Herein we wish to report a facile
sonochemical Michael addition.
As sh own in Table 1 and Sch. 1, Michael additionswere carried out
in good yield catalyzed by KOH in ethanol under ultrasound irradiation.
For example, compound 5j waspreviou sl y prepared in 75% yield cata-
[
11]
lyzed by Ba(OH) in ethanol at reflux temperature for 5 h,
2
whereas
ꢀ
under ultrasonication, 5j wasobtained in 97% yield at 28–38 C for
1.5 h; Compound 3h waspreviou ls y prepared in 72% yield, catalyzed
by NaOH in ethanol at r.t. for 2–4 h,
[
13]
whereaspre es nt procedure
results in the similar yield at 19–24 C for 25 min. In addition, products
ꢀ
4i and 5i were given within 15 min and 30 min, respectively, which
proved 5i wasobtained via the intermediate product 4i. We also did
the experiments in the absence of ultrasound, the addition of 1e and
CH NO (2e) wascarried out in 90% yield ( 3e) using the stirring
3
2
for 2.5 h, while the reaction of 1i and CH COCH CO C H (2i) was
3
2
2
2
5
carried out in 92% yield (4i) using the stirring for 1 h. It is apparent
that Michael addition can be finished in shorter reaction time under
ultrasound.
From these results we can deduce that the yields are, in general,
[
5,11,12]
similar or higher than those described in literature.
Compared

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Michael Addition of Chalcone
355

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Li et al.

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Michael Addition of Chalcone
357
Scheme 1.
with reported, the mainly advantagesof the pre se nt procedure are milder
conditions, higher yield and shorter reaction period.
In conclusion, ultrasound can accelerate the Michael addition of
chalcone with active methylene compound to furnish adducts in high
yield catalyzed by potassium hydroxide with easy work-up.
EXPERIMENTAL
Apparatus and Analysis
[
10]
All chalcones were synthesized according to literature,
melting
1
point, H NMR and MS data agreed to the reported. Diethyl malonate
and ethyl acetoacetate were purified by distillation prior to use. Melting
pointswere uncorrected. Sonication wasperformed in a Shanghai
Branson-CQX ultrasonics cleaner with a frequency of 25 KHz and a
normal power of 500 W. The reaction flask was located in the maximum
energy area in the cleaner and addition or removal of water wasu se d to
control the temperature of the water bath.
General Procedure
To a 50 mL Pyrex flask was added chalcone (1, 1 mmol), active
methylene compound (2, 1.2 mmol), KOH (0.2 mmol), and anhydrous
ethanol (1 mL). The mixture wasirradiated in the water bath of an ultra-

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Li et al.
sonic cleaner at the temperature for the period as indicated in Table 1
sonication was continued until crystals were appeared or chalcone was
(
disappeared indicated by TLC). After cooling a period of time, the pre-
cipitate was isolated by filtration, washed with cool water to neutral,
dried, and crystallized from ethanol. The authenticity of the products
was established by comparison the melting points with literature value.
ACKNOWLEDGMENT
The project was us pported by NSFC (29872011), Natural Science
Foundation of Hebei Province (299080), P.R. China.
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Received in the NetherlandsJanuary 24, 2002

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