Synthesis of 1-(2-hydroxy-phenyl)-3-piperidin-1-yl-propenone by ultrasonic irradiation

Article abstract of DOI:10.1080/00397910500385266

Different 1-(2-hydroxy-phenyl)-3-piperidin-1-yl-propenones have been synthesized by ultrasonic activation from differently substituted 3-formyl chromones and piperidine. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910500385266

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Synthesis of
1‐(2‐Hydroxy‐phenyl)‐3‐piperidin‐1‐yl‐propenone
by Ultrasonic Irradiation
a
a
a
a
N. R. Dalvi , S. N. Shelke , B. K. Karale & H. C. Gill
a
P.G. Department of Chemistry , S.S.G.M. College , Kopargaon,
Ahmednagar, India
Published online: 12 Apr 2007.
To cite this article: N. R. Dalvi , S. N. Shelke , B. K. Karale & H. C. Gill (2007) Synthesis of
1
‐(2‐Hydroxy‐phenyl)‐3‐piperidin‐1‐yl‐propenone by Ultrasonic Irradiation, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 37:8, 1421-1424, DOI:
0.1080/00397910500385266
1
To link to this article: http://dx.doi.org/10.1080/00397910500385266
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Synthetic Communications , 37: 1421–1424, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910500385266
Synthesis of 1-(2-Hydroxy-phenyl)-
-piperidin-1-yl-propenone by Ultrasonic
Irradiation
3
N. R. Dalvi, S. N. Shelke, B. K. Karale, and H. C. Gill
P.G. Department of Chemistry, S.S.G.M. College, Kopargaon,
Ahmednagar, India
Abstract: Different 1-(2-hydroxy-phenyl)-3-piperidin-1-yl-propenones have been syn-
thesized by ultrasonic activation from differently substituted 3-formyl chromones and
piperidine.
Keywords: 3-Formylchromones, piperidine, ultrasonic irradiation
The advantageous use of ultrasound irradiation for activating various reactions
is well documented in the literature for procedures such as synthesis of azoles
[
and diazines, Reformatsky reaction, oxidation of substrates such as hydro-
1]
[2]
[
3]
[4]
quinones,
conversion of nitro compounds to carbamates,
pinacol
[
5]
[6]
[7]
coupling, Ullmann condensation, and Suzuki cross-coupling. The wave-
length of ultrasound is much larger than molecular dimensions, so sound does
not cause such chemistry in a direct interaction. The sonochemistry arises
from the physical phenomenon of acaustic cavitations: the formation, growth,
and implosive collapse of bubbles in liquids irradiated with high-intensity
sound. During the final stages of cavitation, compression of the gas inside the
[8]
bubbles produces enormous local heating and high pressures. Ultrasound-
assisted organic synthesis gives excellent yields compared to traditional
synthesis; it can dramatically affect the rates of chemical reactions and is
[9]
helpful for a large number of organic transformations.
Received July 22, 2005
Address correspondence to H. C. Gill, P.G. Department of Chemistry, S.S.G.M.
College, Kopargaon, Ahmednagar 423 601, India. E-mail: chgill50@yahoo.com
1
421

1
422
N. R. Dalvi et al.
Among the different functionalized chromones, 3-formylchromones
occupy a unique position because they can be transformed into various
[
10]
heterocycles by reactions with different nucleophiles.
when treated with phenyl hydrazine gives 1-phenyl-4-(2-hydroxy benzoyl)
3-Formylchromone
[
11]
[12]
pyrazoles,
whereas 3-formylchromone when treated with piperidine
under reflux gives 1-(2-hydroxy-phenyl)-3-piperidin-1-yl-propenone. Emino-
ketones are versatile synthones that can be converted to a variety of
[
13]
heterocyclic compounds.
piperidin-1-yl-propenone, was utilized for the synthesis of important
The title compound, 1-(2-hydroxy-phenyl)-3-
[14]
bioactive organophosphorous compounds.
Advantages of ultrasound irradiation in organic synthesis and the utility
of the title compound prompted us to prepare 1-(2-hydroxy-phenyl)-3-
piperidin-1-yl-propenones by the reaction of piperidine on 3-formylchro-
mones under the influence of ultrasound irradiation. Methods of preparation
[12]
of 1-(2-hydroxy-phenyl)-3-piperidin-1-yl-propenone reported
were time consuming (they require 3 h of vigorous heating).
earlier
In the present work, a number of 3-formylchromones are treated with
piperidine in dry ethanol under the influence of ultrasound irradiation. By this
method, the time required for completion of the reaction is less and yields are
better than at room temperature, hence no vigorous heating is required. Piperi-
dine reacts with 3-formylchromones by attacking the electron-deficient center
of the C carbon, and the probable mechanism may be as follows:
2
The required 3-formylchromones are synthesized by Vilsmeier–Haack
reaction on variously substituted 2-hydroxyacetophenones.

1-(2-Hydroxy-phenyl)-3-piperidin-1-yl-propenone
1423
EXPERIMENTAL
Melting points were determined in open capillaries in a paraffin bath and are
uncorrected. The reactions were monitored on TLC. IR spectra were recorded
1
in KBr discs on an FTIR instrument. H NMR was recorded on Varian
3
00-MHz instrument with DMSO as a solvent and TMS as an internal
standard. The chemical shift values are in dpm. A mass spectrum was
recorded on a Kratos MS 80 mass spectrometer. Experiments under ultrasound
irradiation were carried out in an ultrasonic cleaner, model EN-20U-S, manu-
factured by Enertech Electronics Pvt. Ltd., Mumbai, India, that has a
maximum power output of 100 W and a 33 KHz operating frequency.
General Procedure for the Synthesis of 1-(2-Hydroxy-phenyl)-
-piperidin-1-yl-propenone by Ultrasonic Irradiation
3
3
1
3
-Formylchromone (0.001 mol) and piperidine (0.002 mol) were taken in
0 mL of dry ethanol and subjected to ultrasonic irradiation for about 25 to
0 min. After completion of the reaction (checked by TLC), contents were
poured over crushed ice. The solid thus obtained was separated by filtration,
washed with water, dried, and crystallized with alcohol to get the title
compound (Table 1).
Table 1. Characterization data of the synthesized compounds
Lit.
[
12]
Time
(min)
Yield
(%)
Mp
(8C)
yield
(%)
No.
R1
R2
R3
1
2
3
4
5
6
7
8
9
H
H
H
H
Cl
F
25
24
28
23
22
20
28
25
28
82
81
85
80
75
86
79
84
86
156
139
145
159
136
164
151
128
132
78
—
80
—
—
—
—
77
—
H
H
Me
Cl
Br
Cl
Me
H
H
Me
H
H
Cl
Me
H
H
H
H
H
H
Et
Note: Purity of compounds was determined by TLC. Compounds
were purified by crystallization with gl. acetic acid. All the products
1
were characterized by Mp, IR, H NMR, and mass.
Spectral Data of Representative Examples
2
1
1
Entry 3, IR (in cm ): 3400, 1627, 1586, and 1537. H NMR (in dpm): 1.85 d
s, 6H), 2.30 d (s, 3H), 3.40 d (s, 4H), 5.80 d (d, 1H, J ¼ 15 Hz), 6.85 d to 7.40 d
(

1
424
N. R. Dalvi et al.
(
m, 3H), 7.80 d (d, 1H, J¼ 15 Hz), 13.75 d (s, 1H). Entry 5, Mass (m/z):
46.1.
2
ACKNOWLEDGMENT
Authors are thankful to Principal G. T. Sangale, S.S.G.M. College,
Kopargaon, Ahmednagar, India, for providing necessary facilities and
constant encouragement.
REFERENCES
1. Kidwai, M.; Venkataramanan, R.; Dave, B. Potassium carbonate, a support for the
green synthesis of azoles and diazines. J. Heterocycl. Chem. 2002, 39, 1045.
2. Ross, N. A.; Bartsch, R. A. Sonochemical Reformatsky reactions of a-bromoester
with sym-(keto)dibenzo-16-crown-5. J. Heterocycl. Chem. 2001, 38, 1255.
3. Singh, V.; Sapehiyia, V.; Kad, G. L. Ultrasonically activated oxidation of hydro-
quinones to quinones catalysed by ceric ammonium nitrate doped on metal
exchange K-10 clay. Synthesis 2003, 2, 198.
4
. Chandrashekhar, S.; Narsihmulu, C.; Jagadeshwar, V. Ultrasound promoted “one-
pot” conversion of nitro compounds to carbamates. Synlett 2002, 5, 771.
. Li, J.-T.; Bian, Y.-J.; Zang, H.-J.; Li, T.-S. Pinacol coupling of aromatic aldehydes
and ketones using magnesium in aq. ammonium chloride under ultrasound. Synth.
Commun. 2002, 32 (4), 547.
5
6
. Robin, M.; Pique, V.; Faure, R.; Glay, J. Ultrasonic irradiation of the Ullmann con-
densation: Application to the preparation of dioxolo, dioxino, cyclopent, and
imidazolo anthranilic acid derivatives. J. Heterocycl. Chem. 2002, 39, 1083.
. Rajagopal, R.; Jarikote, D. V.; Srinivasan, K. V. Ultrasound-promoted Suzuki
cross-coupling reactions in ionic liquid at ambient conditions. Chem. Commun.
7
2
002, 61, 616.
8
9
. Morris, S. Photochemistry and Sonochemistry; Ivy Publishing: Delhi, 2003.
. Ahluwalia, V. K.; Kidwai, M. New Trends in Green Chemistry; Anamaya:
New Delhi, 2004.
1
1
0. Ghosh, C. K. Chemistry of 4-oxo-4H-[1]benopyran-3-carboxaldehyde.
J. Heterocycl. Chem. 1983, 20, 1437.
1. Ghosh, C. K.; Mukhopadhyay, K. K. Reaction of 4-oxo-4H-[1]benzopyran-3-
carboxaldehyde with phenyl hydrazine and formation of 1-phenyl-4-(2-hydroxy
benzoyl) pyrazoles. J. Indian Chem. Soc. 1978, LV, 52.
12. Ghosh, C. K.; Khan, S. Defunctionalization of 4-oxo-4H-[1]benzopyran-3-
carboxylic acid and 3-carboxyaldehyde. Synthesis 1981, 9, 719.
13. Mousawi, S. A.; John, E.; Kandery, N. A. Synthesis and chemical reactivity of
2
-(4-dimethylamino-2-oxobut-3-enyl)-isoindole-1,3-dione and of 4-(4-dimethyl-
amino-2-oxobut-3-enyloxy)-2H-phthalazin-1-one. J. Heterocycl. Chem. 2004,
1 (3), 381–385.
4
1
4. Joshi, N. S.; Karale, B. K.; Jagtap, A. P.; Shinde, S. M.; Bhirud, S. B.; Gill, C. H.
Synthesis and characterization of some heterocyclic organophosphorus
compounds. Indian J. Heterocycl. Chem. 2003, 13 (2), 151–154.