Fly-ash : H2O assisted Aldol condensation : effect of solvents on the synthesis of some aryl (E) 2-propen-1-ones

ANN ALES

UNIVERSITATIS MARIAE CURIE-SKLODOWSKA LUBLIN - POLONIA

VOL. LXVII, 1-2 SECTIOAA 2012

Fly-ash:H20 Assisted Aldol Condensation: Effect of Solvents on the Synthesis of Some Aryl (. E )

2-propen-1-ones

G. Thirunarayanan

Department o f Chemistry, Annamalai University, Annamalainagar-608002, India, dretnaravanan@email.com

Some series of aryl (E) 2-propen-1-ones have been synthesized by Fly-ash:H20 catalyzed aldol condensation of aryl methyl ketones and substituted benzaldehydes at reflux condition in atmospheric pressure. The yields of chalcones are higher than 60%.

These chalcones were characterized by their physical constants and spectral data, for known compounds their purities were checked with the physical constants and spectral data earlier published in the literature. The effects of solvents on the product have been studied.

Keywords: Aryl (E) 2-propen-1-ones, Fly-ash:H20 , IR and NMR spectra, Solvent effects

1. INTRODUCTION

Homogeneous and heterogeneous catalytic Aldol and Crossed-Aldol condensation is an important powerful tool for the formation of carbon- carbon bond in synthesis of many kinds of carbonyl compounds [ 1, 2].

Homogeneous thermal aldol reaction is found to be very slow and took longer time with low yields due to the complication o f separation of catalyst and product.

However, the heterogeneous thermal reactions are good because the rate of the reaction is fast, the reaction time is short and yield is high with

easy isolation of products from the catalyst. Various catalysts have been used for synthesizing chalcones such as silica-sulphuric acid [3,4], anhydrous zinc chloride [5], Clay [6], ground chemistry catalysts- grinding the reactants with sodium hydroxide [7], aqueous alkali in lower temperature[8], solid sulphonic acid from aqueous alkali in lower temperature [9], solid sulphonic acid from bamboo [9], barium hydroxide [ 10] anhydrous sodium bicarbonate [11], microwave assisted synthesis [12], and sulfated titania [13].

Chalcones possess various multipronged activities such as antimicrobial [14], antidepressants [15], antiplosmodial [16], anti-aids [17] and insect antifeedant activities [18-20]. In the present investigation, the author wishes to report a new catalyst Fly-ash:H20 for synthesizing chalcones by Crossed-Aldol condensation reaction. The yields of chalcones are more than 80%.

The synthesized chalcones were characterized by their physical constants, Mass, IR and NMR spectral data as they were unknown compounds so far. The purities of the known synthesized chalcones have been checked by their physical constants and their spectral data earlier published in literature. The effects of solvents on these reactions have been studied. 2

2. EXPERIMENTAL Material and methods

All chemicals used were purchased from Sigma-Aldrich Corporation (St. Louis, MO, USA) and E-Merck chemical company (Merck Limited, Mumbai, India). Melting points of all pyrazolines have been determined in open glass capillaries on Mettler FP51 melting point apparatus (Mettler-Toledo India Private Limited, Mumbai, India) and are uncorrected.

Infrared spectra (KBr, 4000-400 cm-1) have been recorded by AVATAR-300 Fourier transform spectrophotometer (Thermo Nicolet, USA). The NMR spectra of all imines were recorded by Bruker AV400 spectrometer (BRUKER AXS GMBH, Karlsruhe, Germany), operated 400 MHz frequency for recording 'H and 100 MHz for 13C NMR spectra in CDCI3 solvent using TMS as internal standard.

Electron impact (70 eV) and chemical ionization mode FAB+ mass spectra have been recorded by VARIAN-SATURN 2200 GC-MS spectrometer (Varian 92 Medical Systems, Palo Alto, CA, USA).

Synthesis of chalcones

An equi-molar quantities o f aryl methyl ketones (2 mmol) and substituted benzaldehydes (2 mmol), Fly-ash (0.5 g) with 20 cm3 o f water [20, 21] (Scheme 1) were refluxed for 4 h. and the completion o f the reaction was monitored by thin layer chromatography. After completion of the reaction, the solid product was separated by filtration. Afterwards, the product was purified by column chromatography using dichloro- methane and ethyl acetate mixture as eluent.

o

R CH3

Fly-ash:H20 Reflux, 6h

R = C6H5, 4 -N 0 2-C6H4, 4-X-l-naphthyl, 6-X-2-naphthyl, 9H-Fluorene 5-X-2-thienyl, 1-Pyrene

R' = Substituted benzaldehydes

Scheme 1. Synthesis of aryl chalcones by fly-ash:H20 catalyzed aldol conden­

sation.

3. RESULTS AND DISCUSSION

The waste and harmful air pollutant fly-ash containing many chemical species such as [12, 21-24] Si02, Fe203, AI2O3, CaO, MgO and insoluble residues. This pollutant is used as useful catalyst for organic synthesis. Due to the presence o f the above said species, they assisted the aldol condensation in aqueous phase reaction between aryl methyl ketone and aldehydes.

Therefore, the author has attempted to synthesize aryl chalcones by Crossed-Aldol condensation between aryl methyl ketones and benzal­

dehydes in the presence o f fly-ash catalyst under refluxed condition in room temperature and pressure (Scheme 1). Quantitatively, 2 mmol of aryl ketones such as 4-X-phenyl methyl, 4-X-l-naphthyl methyl, 6-X-2- naphthyl methyl, 9H- Fluorene-2-methyl and 5-X-2-thienyl (X = electron donating or electron withdrawing substituents), 2 mmol of substituted benzaldehydes, 0.5 g of fly-ash and 20 cm3 o f water were refluxed for 4h and produced the respective chalcones.

The proposed general mechanism of this reaction is shown in Fig. 1.

It follows the removal o f water and proton giving the product. The yields

o f chalcones are more than 60%. Analytical, physical constants, yield and mass fragments (m/z) are presented in Table 1.

®

1 Acidic site of

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A = /

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i

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Fig. 1. The proposed mechanism for the synthesis of chalcones by fly-ash:H20 catalyzed aldol condensation.

Table1. Analytical andmass spectral dataof chalcones synthesizedbyFly-ash- H2SO4 catalyzedaryl methyl ketones andsubstituted benzaldehydes reaction of the type R—CO—CHi + R'—CHO —» R—CO—CH^H—R' under microwave irradiation.

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