3rd International Chemical Engineering and Chemical Technologies Conference Nov.30-Dec.

1, 2015, Istanbul, Turkey

Synthesis and Characterization of Mg-Al-CO3-LDH: a Highly Efficient Catalyst for the Synthesis
of 3,4-Dihydropyrimidin-2(1H)-ones and Thiones analogs by Biginelli Reaction under Solvent-Free Conditions

Mustapha DIB, Soufiane AKHRAMEZ, Abdellatif ESSOUMHI, Hajiba OUCHETTO, Khadija OUCHETTO,
Abderrafia HAFID and Mostafa KHOUILI
Organic and Analytical Chemistry Laboratory , Faculty of Science s and Technologies Beni-Mellal (FST-BM), Sultan Moulay Slimane University , PO Box 523,
23000-Beni-Mellal, Morocco.
E-mail: d.mustapha@usms.ma

Abstract
INTRODUCTION
Synthesis of 3,4-dihydropyrimidin-2(1H)-ones/thiones (DHPMs), a multi-component Biginelli reaction, has been carried out by using ethyl acetoacetate, aromatic aldehydes, substituted
urea/thiourea and in the presence of Mg-Al-CO3-LDH as a reusable solid catalyst. The catalyst was prepared by a co-precipitation method at a pH of 10, with ratio of Mg2+/Al3+ = 3 molar
ratio constant.
The main advantages of the method are good yield, short reaction times, moderate temperature (90°C), catalyst reusability and environmental friendliness. Mg-Al-CO3-LDH is easy to
separate from the reaction mixture and to recycle and reused without decreasing the reaction yield. X-ray Diffraction and infrared spectroscopy were used for characterization of the
catalyst.

METHODS AND MATERIALS

1- Catalyst preparation
The catalyst was prepared by the co-precipitation method [1] at pH=10.0 ± 0.2

The x-ray diffraction analysis of the resulting product showed it to have a layered double hydroxide

structure. the peak (00l) generally observed for the lamellar compounds, with good cristanility [2].
Solution B
Solution A
Na2CO3 + NaOH
MgCl2.6H2O + AlCl3MgCl2.9H2O
2-2 Infrared spectroscopy:
At room temperature, the two
The spectra were recorded with 2 cm-1 resolution in the range of 4000–400 cm-1 :
solutions (A and B) were mixed
drop by drop and kept under
vigorous mechanical stirring at a
pH of 10.
 The IR spectra of Mg–Al–CO3–LDH showed characteristic absorption bands of CO3, metal-oxygen

The reaction was carried out at and OH group at 1385 cm-1, 500-1000 cm-1 and 3500 cm-1 respectively.
reflux for 17 h.

The precipitate was filtered and washed with water 3- Biginelli Reaction catalyzed by Mg/Al–CO3–LDH
The gel obtained was dried at 80°C General procedure :

In a typical general experimental procedure[3], a mixture of aromatic aldehyde, ethylacetoacetate and

0% 2% 6%
urea or thiourea were made to react in the presence of the catalyst Mg-Al-CO3-LDH as shown in
MgAlCO3-LDH
reaction scheme.

O O 10% 14% 16%

Fig 1: Preparation steps of Mg–Al –CO3–LDH

O
H 3C O CH 3
2- Catalyst characterization Mg-Al-CO 3 -LDH
B-keto ester H 3C O NH
2-1 X-Ray analysis: O 90°C; Reflux
X
Counts
Mg-Al-HDL3.raw
+ H 3C N X
H
003

3000
H 2N NH 2
Mg-Al-LDHs (Mg /Al=3)
Fig 2: X-ray Diffractogram corresponding to Mg–Al –CO3–LDH X= O,S 68 ~80 %
Urea or Thiourea Aromatic aldehyde

2000
Intenssity (u.a)

Scheme 1. Mg–Al–CO3–LDH -catalyzed synthesis of 3,4-dihydropyrimidin- 2(1H)-ones and -thiones.

006

RESULTS AND DISCUSSION

1000
012

110

The progress of the reaction was monitored by thin layer chromatography. All the reactions were
113
015

018

116

completed with 35 minutes of reaction time under solvent free, with very good yields (68-80%) of the
0

10 20 30 40 50 60 70
corresponding product.
Position [°2Theta]

Fig 2: X-Ray Diffractogram of Mg–Al –CO3–LDH

Conclusion
The Mg-Al-CO3-HDL material was prepared by a coprecipitation method at constant pH (10 ± 0.2), with a ratio Mg / Al = 3. The catalytic protocol that we have used in the classical Biginelli reaction
is simple, rapid, high yielding and environmentally friendly.

References
[1] Kovanda F, Rojka T, Dobešová J, Machovič V, Bezdička P, Obalová L, Jirátová K, Grygar T. J Solid State Chem, 2006, 179: 812
[2] R.L .Frost, H .J.Spratt, S. J. Plmer . Spectrochimica Acta Part A:Mol. And Biomol Spectr . , 72 (2009) 984.
[3] P. Biginelli, “Derivati aldeidureidici degli eteri acetil-ed ossalacetico,” Gazzetta Chimica Italiana, vol. 23, pp. 360–416,1893.