Experimental study of synthesis polymer based on maleic acid and 2-methylquinoxaline 1,4-dioxide using photocatalysis

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Experimental study of synthesis polymer based on maleic acid and 2-methylquinoxaline 1,4-dioxide using photocatalysis

Kawthar Ghanoum PhD student

Homs, Syria. Adnan Kodlaa Faculty of Science

Department of Chemistry, Al-Baath University

Abstract

In this research, a polymer was synthesized by reaction between maleic acid and 2-methylquinoxaline 1,4-dioxide(Q) at 254 nm, where in the first step maleic acid reacted with (Q) and formed the derivative (QMA), which reacted in the second step with maleic acid molecules and formed the polymer chain, by forming carbon-carbon bridges and removing water molecules. A mechanism for the reaction was suggested. The structure of the polymer was elucidated by spectroscopic analysis (IR, UV, and 1H NMR).

Key words: quinoxaline, polymer, mechanism, spectroscopic analysis.

Экспериментальное исследование синтеза полимера на основе малеиновой кислоты и 1,4-диоксида 2-метилхиноксалина с использованием фотокатализа

Аннотация

В этом исследовании полимер был синтезирован по реакции между малеиновой кислотой и 1,4-диоксидом 2-метилхиноксалина (Q) при 254 нм, где на первой стадии малеиновая кислота прореагировала с (Q) и образовала производное (QMA), которое на втором этапе прореагировал с молекулами малеиновой кислоты и образовал полимерную цепь, образовав углерод-углеродные мостики и удалив молекулы воды. Механизм реакции был определен. Структура полимера была выяснена с помощью спектроскопического анализа (ИК, УФ и 1Н ЯМР).

Ключевые слова: хиноксалин, полимер, механизм, спектроскопический анализ.

Introduction

Photochemistry and photophysics represent a modern branch of science, at the interface between light and matter and at the crossroads of several disciplines including chemistry, physics, material science, ecology, biology, and medicine[1]. In our daily life, we are surrounded by products obtained with the aid of photochemistry and photophysics and by devices that exploit photochemical and photophysical processes to perform useful functions in a variety of places, from industries to hospitals[2]. Some of the main applications of photochemistry are polymerization, photohalogenation, photosulfonization, photolysis, photooxidation and photocyclic addition reactions[3].

In our previous works[4,5], we investigate, the optimal structures for reactants and their electronic, photochemical and spectral properties. using the density functional theory (DFT / B3LYP (6-311 ++ G (2d)) and time depended density functional theory (TD-DFT/B3LYP (6-311++G (2d)).

In the present work a polymer based on maleic acid and 2-methylquinoxaline 1,4- dioxide Using Photocatalysis were prepared and the mechanism for the reaction was proposed where maleic acid[6],is multifunctional chemical intermediates that find applications in nearly every field of industrial chemistry. Maleic acid is important raw material used in the manufacture of phthalic-type alkyd and polyester resins, surface coatings, lubricant additives, plasticizers (qv), copolymers (qv), and agricultural chemicals.

Also, Quinoxaline and its derivatives have been extensively synthesized for their ability of antibiotic, antiviral, anti-carcinogenic, anti-bacterial and other medicinal properties[7,8]. The application of these derivatives do not end with the disease curing drugs, but also extends as industrially useful elements like dyes and electroluminescent materials[9,10].

Apparatus Section

Spectrum NMR proton device 400 MHz model Bruker by Switzerland company optical absorption spectrum infrared device model FT-IR-4100 from the Japanese company Jasco, T80+ UV/Vis spectroscopy (PG Instruments Ltd),, Silica gel dedicated to Merck chromatographic columns, WD-9403E Hand Held UV Lamp from Beijing Liuyi Instrument Factory.

synthesis polymer maleic acid

Chemicals Materials

2- methyl quinoxaline 1,4-dioxide was prepared in the laboratory, Maleic Acid 99.5% (by BDH), dichloromethane 99.0% (by SIGMA- ALDRICH), acetonitrile 99.9% (by panreac), methanol 99.99% (by ACROS ORGANICS), chloroform (by BDH).

Experimental study

* Synthesis:

2-methyl quinoxaline 1,4-dioxide was reacted with maleic acid using a monochromatic UV light that gives a light length of 254 nm, in a flat cell. The mixture was irradiated for (15min) at room temperature (250C), and a purified product was formed using a chromatographic column containing a fixed phase of silicagel and a moving phase consisting of a mixture (dichloromethane and methanol At a ratio of 80:20), a solid yellow product was obtained after purification, and the molecular structure of the resulting compound was determined using the available spectroscopic methods.

Figure (1): Suggested synthetic route of the product polymer * Infrared Spectra:

Spectrum of polymer is shown in figure (2). A weak absorption band at (3025cm-1) is observed due to the vibration of the C-H bond in the aromatic ring, and another band at (2922cm-1) returns to the aliphatic C-H bond, strong absorption band is noted at (1733cm-1) returns to carbonyl group C = O, absorption bands at (1573 cm-1,1353 cm-1,1254 cm-1), return to: (Ar C = C, N-O, C-O-C), respectively.

Figure (2): IR absorption spectra of the product polymer in (KBr).

* 1H NMR spectroscopic measurements:

The product polymer was further confirmed by 1H-NMR spectroscopy, as shown in figure (3). The characteristic signal around (5 =1.25 ppm) belonged to protons in methyl group CH3, and the signals around (5 = 7.70, 7.53 ppm) belonged to aromatic protons, the signal around (5 = 4.86 ppm) belonged to H4, the signals around (5 = 2.02 ppm) belonged to H5, the signal around (5 = 1.75ppm) belonged to H6, the signals around (5 = 2.88,2.95 ppm) belonged to H7, the signal around (5 = 3.84 ppm) belonged to H2.

Figure (3): 1HNMR spectrum of the polymer(400 MHz, CDC13,Stms = 0 ppm). * Electronic spectral data:

The electronic spectra of the resulting compound in methanol solution has two bands at (210 nm) assigned to (n^ n*) transition in aromatic rings, and (370 nm) assigned to (n^ n*) transition returns to carbonyl group C = O in the compound Figure (4). Table (1) shows Values of wave lengths and absorption in UV spectrum.

Wavelength [nm]

Figure (4): UV spectra of product polymer.

Conclusions

In this work, we synthesized a polymer based on maleic acid and 2- methylquinoxaline 1,4-dioxide using photocatalysis and the mechanism for the reaction was proposed. We recommend studying some polymer properties such as optical properties and semiconductors for use it in a variety applications.

References

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