Synthesis and characterization of two coumarin fluorescent dyes containing a chalcone moiety

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Synthesis and characterization of two coumarin fluorescent dyes containing a chalcone moiety

Фадия Алхай Хуссьен Аспирант, факультет наук Химический факультет Университета Аль-Баас,

Хомс, Сирия Пятница мирза

Арабский частный научно-технический университет

Фармацевтический факультет

Хама, Сирия Рушди Мадвар Химический факультет Факультет наук, Университет Аль-Баас

Abstract

Two of coumarin-chalcone hybrids were synthesized via Claisen- Schmidt condensation between 3-acetylcoumarin with benzaldehyde and 4-chloro benzaldehyde respectively.

The progress of the reaction was monitored by TLC and The synthesized compound structures were identified and confirmed by UV-Visible, FT-IR and 1H -NMR and 13C-NMR. spectral analysis respectively.

Keywords: coumarin, chalcone, Claisen-Schmidt condensation.

Аннотация

synthesis coumarin chalcone hybrid chemical

СИНТЕЗ И ХАРАКТЕРИСТИКА ДВУХ ФЛУОРЕСЦЕНТНЫХ КРАСИТЕЛЕЙ КУМАРИНА, СОДЕРЖАЩИХ ФРАГМЕНТ ХАЛКОНА

Два из гибридов кумарин-халкон были синтезированы посредством конденсации Клайзена-Шмидта между 3-ацетилкумарином с бензальдегидом и 4-хлорбензальдегидом соответственно.

Ход реакции контролировали с помощью ТСХ и структуры синтезированного соединения идентифицировали и подтверждали с помощью УФ-видимого, ИК-Фурье и 1Н-ЯМР и 13С-ЯМР, спектральный анализ соответственно. Ключевые слова: кумарин, халкон, конденсация Кляйзена-Шмидта.

Introduction

Coumarin and its derivatives have attracted much attention due to their various pharmacological activities, such as antiviral, anti-inflammatory and antitumour activity.1 Furthermore, coumarins are widely used as laser dyes, nonlinear optical chromophores, fluorescent probes, fluorescent whiteners and solar energy collectors due to their outstanding optical properties, including superior photostability, large Stokes shifts and high quantum yields[1-3].

Chalcones are one of the major classes of organic compounds and have been extensively investigated due to their variety of applications. They are reported to have antioxidant, antitumour and anti-inflammatory activities. Furthermore, chalcones exhibit excellent nonlinear optical properties and they can be used in organic light-emitting diodes[4,5]. Therefore, hybridise of a coumarin nucleus with a chalcone moiety should likely to lead to a hybrid compound with significant properties. Indeed, coumarin-chalcone hybrids have been reported to have antiinflammatory, antioxidant and antiviral activities.[6,7] They also show good thermal stability and fluorescent properties. beside that the recent researches have repporead that the fusion of a chalcone moiety to the coumarin ring is quite promising for the synthesis of derivatives with an extended spectral range (270-600 nm for the absorption band and 400-700 nm for the emission band) and produce substances that can be used as blue, green, and red dopants in organic light-emitting diodes (OLEDs). Many ketocoumarin-based electroluminescent (EL) materials have been and are currently being developed [8-10]. The aim of this work is hybridise coumarin and chalcone moieties to improve and enhance the pharmalogical properties such as antimicrobial, antitumor, antioxidant, antimalarial and antifungal activities [10-14] and to enhance and improve the fluorescent properties of obtained dyes wich used as fluorescent dyes for synthetic fibres

Experimental

Apparatus:

spectrum NMR proton and carbon device 400 MHz model Bruker by Switzerland company.Optical absorption spectrum infrared device model FT-IR-4100 from the Japanese company Jasco. VIS and UV absorption spectrum absorption model POP Japanese company Jasco.

Raw Materials and Reagents:

4-chloro benzaldehyde,benzaldehyde , Salicyaldehyde , ethyl aceto acetate, piperidine, ethanol (Sigma-Aldrich & Merck)

Experimental Procedure: synthesis of 3-acetyl coumarin (3)

The mixture of Salicyaldehyde (l) (0.2M, 4.28 ml) and ethyl aceto acetate (2) (0.2M, 5.13 ml) was taken in a beaker, with continuous stirring. After 2 mints 5 to 6 drops of catalyst piperidine was added in the reaction mixture with vigorous shaking. After 30 minutes yellow precipitate was separated out. The precipitate was filtered off, washed and recrystallized with ethanol .

Synthesis of coumarin-chalcone hybrids (4a,4b) general procedure:

A mixture of 3-acetyl coumarin (3) (0.01mol) and corresponding aldehyde (0.01mol) and 10 mL ethanol taken in a round bottom flask. Then 4 to 5 drops of Piperidine was added to it. The reaction mixture allowed refluxing on 5 -8 hour at 80oC (The formation of product was monitored by TLC). The reaction mixture was poured into ice cold water and then it was neutralized by hydrochloric acid. The yellow colour solid productes was filtered and recrystallized by using ethanol.

3- acetyl coumarin (3): Yellow solid; yield 76%; m.p. 119-122 °C; IR (KBr) (cm-

1) : 2945(Aromatic C-H stretching),1728.29(C=O(ester)), 1627.29(C=O(Exo cyclic ketone)), 1599.23 C=Cstr.(Aromatic),1351(C-Cstr), 752(C-Hout plane bending), 1157.28 (C-O str).; UV-visible (k max: nm) 298 (n ^ n * transition), 340 (n ^ n * transition) 1H NMR (400 MHz, DMSO-d6): 5 2.31 (s, 3H, CH3), 7.34-7.68 (m, 4H, Benzo fused coumarin-H),8.45(s, 1H, Coumarin-H).

3-(3-(4-Chloro phenyl)acryloyl)coumarin (4b): Yellow solid; yield 71%; m.p. 189-191 °C; IR (KBr) (cm-1) 1618, v(C=O, a, y0-unsaturated ketone), 1732, v(C=O, lactone carbonyl of coumarin); UV-visible (k max: nm)286 (n ^ n * transition), 306(n ^ n * transition) ) 1H NMR (400 MHz, DMSO-d6) 5 7.68 (3H, m,2H for p-substituted phenyl ring and 1H for aromatic proton), 5 7.55 (1H, m, aromatic protons), 5 7.34 (2H, m, aromatic proton), 5 7.62 (2H, m, p-substituted phenyl ring), 5 7.45 (1H, d, J = 7.8 CH=CH- protons), 5 7.82 (1H,J=15.5, d, CH=CH- protons), 5 8.57 (1H, s, C4-H).

3-(3-phenylacryloyl)coumarin (4a): Yellow solid; yield 77%; m.p. 170-172 °C; IR (KBr) (cm-1) 1620, v(C=O, a, y0-unsaturated ketone), 1738, v(C=O, lactone carbonyl of coumarin); UV-visible (k max: nm)290 (n ^ n * transition), 315(n ^ n * transition) ¹H NMR (400 MHz, DMSO-d6) 5 8.65 (s, 1H), 7.92 (d, 1H, CH=CH- protons), 7.75 (m , 4H phenyl ring protons ), 7.64 (d, J = 16.0 Hz, CH=CH- protons, 1H), 7.46 (m, 5H phenyl ring protons).

Result and disscusion

The coumarin Fluorescentes dyes were synthesized by two steps in the first step 3-acetyl coumarins 3 were prepared by Knoevenagel condensation of salicylaldehyde 1 with ethyl acetoacetate 2 in the presence of piperidine in ethanol with 88% yields Scheme 1.

Scheme 1 Synthesis of 3- actyl coumarin

In the second step The Claisen-Schmidt condensation of 3-actyl coumarin with benzaldehyde and 4-chloro benzaldehyde respectively yielded the two coumarin- chalcone hybrids (4a,4b) scheme 2

Scheme 2 Claisen-Schmidt condensation of 3-actyl coumarin with benzaldehydes

UV absorption and FT- IR spectra of compound (3, 4a,4b) has been provided a preliminary idea in confirmation the formation of productes. According to the UV spectrum, presence of peaks at 286 nm and 306 nm (in compound 4b) and 290 nm and 315 nm ( in compound 4a)clearly showed that these two compoundes has - CH=CH- group and hetero atom respectively . According to the FT-IR, presence of peak at 1627.29 cm_1 has clearly, the utilization of starting coumarin transform in to the product. Further, the corresponding peaks at 2945, 1728.29,1627.29,1599.23,1351,7 52 and 1157.28 cm_1 have been related to - Ar CH str, C=O ester (str), C=O Exo cyclic ketone (str), C=C str.(Aromatic), C-C str. (exo cyclic),(C-H out plane bending) and (C-O str) respectively in the compound (3)

Similarly, the FTIR, presence of peak at 1618 cm_1 has clearly, the utilization of starting materials transform in to the product. Further, the corresponding peaks at 1618, v(C=O, a, y^-unsaturated ketone), 1732, v(C=O, lactone carbonyl of coumarin) in compound (4b) and peaks at 1620 v(C=O, a, y0-unsaturated ketone),1738 v(C=O, lactone carbonyl of coumarin) in compound (4a) Respectively .In the proton NMR spectra the two dyes showed characteristic one proton singlet at 8.5-8.6 ppm for the proton at the 4-position of coumarin ring.The characteristic alkene protons on the chalcone unit appeared as doublets at 7.64 and7.92 ppm in (4a) and at 7.45and 7.82 ppm in (4b) respectively. These alkene protons showed a typical coupling constant value of 15.5-16 Hz confirming the trans-geometry of the alkene bond.

Conclusions: In this work, we synthesized two of coumarin Fluorescent Dyes containing a chalcone moiety which have high pharmalogical properties and fluorescent properties which can used as fluorescent dyes for synthetic fibres

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