Sains Malaysiana 49(11)(2020): 2715-2720

http://dx.doi.org/10.17576/jsm-2020-4911-10

Green Synthesis of Renewable Dimethyl Terephthalate-Like Monomer from Eugenol

(Sintesis Hijau Dimetil Diperbaharu Tereftalat Seakan Monomor daripada Eugenol)

MAULIDAN FIRDAUS¹*, TRIANA KUSUMANINGSIH², ATMANTO HERU WIBOWO¹ & CARISSA HERTININGTYAS³

¹Research Group of Synthesis and Material Functionalization, Universitas Sebelas Maret, Jl. Ir. Sutami 36A Surakarta 57126, Indonesia

²Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Sebelas Maret, Jl. Ir. Sutami 36A Surakarta 57126, Indonesia

³Department of Chemistry, Graduate School, Universitas Sebelas Maret, Jl. Ir. Sutami 36A Surakarta 57126, Indonesia

Received: 5 November 2019/Accepted: 13 May 2020

ABSTRACT

Dimethyl terephthalate, a diester monomer derived from petroleum-based resources, plays important role in the production of polyester such as polyethylene terephthalate (PET), resins for polyester, fibres, and films as well as engineering polymers. High demand on PET together with environmental concerns require to find alternative for renewable monomers urgently whenever or wherever to substitute the exhausting crude oil-based monomers. A simple and highly efficient method to prepare PET analogue monomer, methyl 2-[2-methoxy-4-[3-(2-methoxy-2-oxoethyl)]thiopropyl]phenoxy acetate (4), from renewable eugenol is described. The key step involves successive Williamson etherification, esterification, to be followed by thiol-ene reaction. Remarkably, it turned out that the thiol-ene reaction has proven to be effective in the introduction of the ester group to the olefinic substrate without the use of solvent and initiator leading to diester 4. The technique offered here comprises advantages i.e. excellent yields, mild reaction condition, and easy to perform, thus, provide a sustainable alternative to synthesize diester from eugenol.

Keywords: Dimethyl terephtalate-like; esterification; eugenol; thiol-ene addition; Williamson etherification

ABSTRAK

Dimetil tereftalat ialah monomer diester yang diterbitkan daripada sumber berasaskan petroleum, memainkan peranan penting dalam penghasilan poliester seperti polietilena tereftalat (PET), resin untuk poliester, serat dan filem serta polimer kejuruteraan. Permintaan tinggi ke atas PET serta kebimbangan persekitaran memerlukan pencarian alternatif monomer diperbaharu secepat mungkin untuk menggantikan minyak mentah berasaskan monomer yang semakin berkurangan. Kaedah yang mudah serta cekap untuk menyediakan monomer analog PET, metil 2-[2-metoksi-4-[3-(2- metoksi-2-oksoetil)]tiopropil]fenoksi asetat (4), daripada eugenol diperbaharu telah dicirikan. Langkah penting melibatkan eterifikasi Williamson secara berturutan, esterifikasi dan diikuti oleh reaksi tiol-ena. Menariknya, ternyata reaksi thiol-ena terbukti berkesan dalam memperkenalkan kumpulan ester kepada substrat olefinik tanpa menggunakan pelarut dan pemula yang menghasilkan diester 4. Teknik yang digunakan memberikan kelebihan seperti hasil yang tinggi, keadaan tindak balas yang sederhana dan mudah dijalankan, dengan memberikan alternatif diperhabaru untuk mensintesis diester daripada eugenol.

Kata kunci: Dimetil tereftalat-analog; esterifikasi; eugenol; penambahan thiol-ena; reaksi eterifikasi Williamson

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*Corresponding author; email: maulidan@mipa.uns.ac.id