Malaysian Journal of Analytical Sciences Vol 25 No 6 (2021): 987 - 997

 

 

 

 

CATALYTIC ACTIVITY STUDY OF SYNTHESISED POLYSTYRENE-SUPPORTED PALLADIUM(II)-HYDRAZONE (CH3) AS CATALYST IN HECK REACTION

 

(Kajian Aktiviti Pemangkinan Paladium(II)-Hidrazon (CH3) dengan Sokongan Polistirena Sebagai Pemangkin dalam Tindak Balas Heck)

 

Najwa Asilah M. Shamsuddin1, Norul Azilah Abdul Rahman1,2, Kumuthini Chandrasekaram3, Yatimah Alias3, Nur Rahimah Said1*

 

1School of Chemistry and Environment, Faculty of Applied Sciences,

 Universiti Teknologi MARA, Cawangan Negeri Sembilan, Kampus Kuala Pilah, 72000 Kuala Pilah, Negeri Sembilan, Malaysia

2School of Chemistry and Environment, Faculty of Applied Sciences,

Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia

3Centre for Ionic Liquids (UMCiL), Department of Chemistry, Faculty of Science,

University of Malaya, 50603 Kuala Lumpur, Malaysia

 

*Corresponding author:  nurra1435@uitm.edu.my

 

 

Received: 13 September 2021; Accepted: 15 November 2021; Published:  27 December 2021

 

 

Abstract

Polystyrene as polymer support has various requirements of catalysts for different chemical reactions due to its accessibility, mechanical robustness, product selectivity, chemical inertness, and facile functionalization. This study focuses on the synthesis of polystyrene-supported palladium(II)-hydrazone complex where the hydrazone ligand with an electron donating group (-CH3) acting as the catalyst in Heck reaction. The first step began with aldehyde functionalization of chloromethylated polystyrene to form PS-CHO. This was then followed by the reaction of PS-CHO with p-toluic hydrazide to form a polystyrene-supported hydrazone ligand (PS-H(CH3)), which was then reacted with palladium(II) chloride to form polystyrene-supported palladium(II) hydrazone catalyst, PS-Pd(CH3). The successfully synthesized PS-Pd(CH3) catalyst was characterized using FTIR, PXRD, FESEM-EDX and AAS. The catalytic performance of PS-Pd(CH3) was tested using Heck reaction between 1-bromo-4-nitrobenzene and methyl acrylate. The percent conversion of reactant to product was determined using GC-FID, where the optimum conversion rate was 99.84 % with 1.0 mmol% catalyst loading, K2CO3 as base and DMA as solvent at 165 °C within a 60-minute reaction time.

 

Keywords:  Heck reaction, hydrazone ligand, polystyrene, polymer support, palladium(II)-hydrazone complex

 

Abstrak

Polistirena sebagai sokongan polimer mempunyai pelbagai kegunaan sebagai pemangkin tindak balas kimia kerana kebolehdapatan, ketahanan mekanik, daya pemilihan produk, lengai secara kimia dan pengfungsian mudah. Kajian ini memberi tumpuan kepada sintesis kompleks paladium(II)-hidrazon dengan sokongan polistirena dengan ligan hidrazon yang mengandungi kumpulan elektron penderma (-CH3) sebagai pemangkin dalam tindak balas Heck. Sintesis dimulakan dengan pengubahsuaian polistirena klorometil dengan fungsian aldehid untuk membentuk PS-CHO. Kajian dilanjutkan dengan tindak balas PS-CHO dengan p-toluik hidrazida untuk membentuk ligan hidrazon dengan sokongan polistirena (PS-H(CH3)). Kemudian, PS-H(CH3) bertindak balas dengan paladium(II) klorida untuk membentuk pemangkin hidrazon paladium(II) dengan sokongan polistirena iaitu PS-Pd(CH3). Kejayaan sintesis pemangkin disahkan dengan menggunakan FTIR, PXRD, FESEM-EDX dan AAS. Keberkesanan pemangkinan PS-Pd(CH3) diuji dalam reaksi Heck antara 1-bromo-4-nitrobenzena dan metil akrilat. Peratus penukaran bahan tindak balas kepada produk ditentukan dengan menggunakan GC-FID, dimana penukaran optimum ialah 99.84% dengan pemangkin 1.0 mmol%, K2CO3 sebagai bes dan DMA sebagai pelarut pada suhu 165 ° C dalam masa tindak balas 60 min.

 

Kata kunci:  tindak balas Heck, ligan hidrazon, polistirena, sokongan polimer, komplek paladium (II) - hidrazon

 

 

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