Malaysian Journal of Analytical Sciences Vol 24 No 3 (2020): 422 - 435

 

 

 

 

EXPERIMENTAL AND DENSITY FUNCTIONAL THEORY INVESTIGATION ON IMINE FORMATION USING MICROWAVE IRRADIATION

 

(Penyiasatan Secara Eksperimen dan Teori Fungsi Ketumpatan ke atas Penghasilan Imina Menggunakan Penyinaran Gelombang Mikro)

 

Fatin Ilyani Nasir^1,2, Wun Fui Mark-Lee³, Yan Yi Chong¹, Mohammad B. Kassim¹, Siti Aishah Hasbullah¹, Douglas Philp⁴, Nurul Izzaty Hassan¹*

 

¹Department of Chemical Sciences, Faculty of Science and Technology,

Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

²Analytical Biochemistry Research Centre,

Universiti Sains Malaysia, 11800 Penang, Malaysia

³Department of Basic Science and Engineering, Faculty of Agriculture and Food Sciences,

Universiti Putra Malaysia, 97008 Bintulu, Sarawak, Malaysia

⁴Department of Chemistry,

Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, USA

 

*Corresponding author:  drizz@ukm.edu.my

 

 

Received: 3 April 2020; Accepted: 10 May 2020; Published:  9 June 2020

 

 

Abstract

Four starting materials comprising of N-(4,6-dimethylpyridin-2-yl)-4-formylbenzamide 1, 4-amino-N-(4,6-dimethylpyridin-2-yl)benzamide 2, 4-amino-2-methylbenzoic acid 3 and 4-formylbenzoic acid 4 react in a pairwise manner through the condensation reaction to give four imine derivatives, Imine 5, 6, 7 and 8. A simple method has been developed for the synthesis of these imine derivatives under microwave irradiation. In addition, these compounds were synthesised also by conventional heating procedures for comparison. All the compounds synthesised were characterised by melting point, infrared, mass spectrometry, ¹H and ¹³C NMR spectroscopy. Comparison between conventional and microwave irradiation was done by comparing total reaction time and percentage yield. The results suggest that microwave-irradiation lead to higher yields within very short reaction times. Compounds 1 and 2 crystallised in the orthorhombic (P2₁2₁2₁ space group) and monoclinic (P2₁/c space group) crystal systems, respectively. The nature of minimal replicator of imine 6 via autocatalytic reaction was calculated using density functional theory (DFT) with the combination of hybrid functional B3LYP and 6-311G(d,p) basis set. The reaction pathway facilitated with the addition of imine 6 or imine 5  equipped with complementary recognition sites of two carboxylic acids and two 4,6-dimethylamidopyridines were predicted to be thermodynamically favourable.

 

Keywords:  imine, condensation, conventional heating, microwave irradiation, density functional theory

 

Abstrak

Empat bahan bermula terdiri daripada N-(4,6-dimetilpiridin-2-il)-4-formilbenzamida 1, 4-amino-N-(4,6-dimetilpiridin-2-il)benzamida 2, asid 4-amino-2-metilbenzoik 3 dan asid 4-formilbenzoik 4 bertindak balas secara berpasangan melalui tindak balas kondensasi untuk menghasilkan empat terbitan imina, imina 5, 6, 7 dan 8. Satu kaedah mudah telah dibangunkan untuk menghasilkan terbitan imina di bawah penyinaran gelombang mikro. Di samping itu, terbitan imina ini turut dihasilkan melalui kaedah pemanasan konvensional sebagai perbandingan. Semua sebatian yang di sintesis dicirikan melalui analisis takat lebur, inframerah, spektrometri jisim, spektroskopi ¹H dan ¹³C RMN. Perbandingan antara kaedah konvensional dan penyinaran gelombang mikro dilakukan dengan membandingkan masa tindak balas dan hasil peratusan. Keputusan ini mencadangkan kaedah penyinaran gelombang mikro memberikan peratusan hasil yang lebih tinggi dalam masa tindak balas yang singkat. Sebatian 1 dan 2 masing-masing menghablur dalam sistem ortorombik (kumpulan ruang P2₁2₁2₁) dan monoklinik (kumpulan ruang P2₁/c). Sifat replikator minimal imina 6 melalui tindak balas autokatalitik telah dikira menggunakan teori fungsi ketumpatan (DFT) dengan menggunakan gabungan asas fungsi hibrid B3LYP dan set asas 6-311G(d,p). Laluan tindak balas dibantu dengan penambahan sebatian imina 6 atau imina 5 yang dilengkapi dengan tapak pengecaman, terdiri daripada dua moieti asid karboksilik dan dua moieti 4,6-dimetilpiridina yang dijangka berada di bawah kawalan termodinamik.

 

Kata kunci:  imina, kondensasi, pemanasan konvensional, penyinaran gelombang mikro, teori fungsi ketumpatan 

 

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