Sains Malaysiana 47(5)(2018): 923–929

http://dx.doi.org/10.17576/jsm-2018-4705-07

 

Experimental and DFT Investigation on the Influence of Electron Donour/Acceptor on the Hydrogen Bonding Interactions of 1-(1,3-Benzothiazol-2-yl)-3-(R-benzoylthiourea)

(Uji Kaji dan Penyiasatan DFT mengenai Pengaruh Penderma/Penerima Elektron pada Interaksi Ikatan Hidrogen dalam 1- (1,3-Benzotiazol-2-yl) -3- (R-benzoylthiourea))

 

MUHD HAFIZI B. ZAINAL¹, WUN FUI MARK-LEE¹, SYAHIDAH MOHD TAHIR¹, ISHAK B. AHMAD¹ & MOHAMMAD B. KASSIM^1,2*

 

¹School of Chemical and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan, Malaysia

 

²Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan, Malaysia

 

Received: 20 September 2017/Accepted: 29 December 2017

 

ABSTRACT

The presence of two different chromophores in benzothiazole molecule namely benzothiazole and aromatic rings lead to interesting chemical and biological properties that attract more researches on the compounds. Three new benzothiazolyl-benzoythiourea compounds namely 1-(1,3-benzothiazol-2-yl)-3-(benzoylthiourea) (BBT), 1-(1,3-benzothiazol-2-yl)-3-(4-chlorobenzoylthiourea) (BBT-4Cl) and 1-(1,3-benzothiazol-2-yl)-3-(4-methoxybenzoylthiourea) (BBT-4OCH₃) with different electron withdrawing substituents (R) at the para positions on the benzene ring of benzoylthiourea ring have been synthesized from the reaction of R-benzoyl isothiocyanate (R= H, Cl, and OCH₃) and 2-aminobenzothiazole. The compounds were characterized by spectroscopic techniques (infrared, 1H proton NMR and UV-Vis). The IR spectra showed the frequency signals of n (C=O), n (C=S), n (N-H) at 1664-1673, 1238-1249 and 3031-3055 cm-1, respectively. The 1H proton NMR spectra showed the presence of N-H amine and amide signals in the region of (12.14-12.35) and (14.17-14.43) ppm, respectively. The proton signals of the two benzothiazole and benzoylthiourea moieties appear at 7.08-8.16 ppm. A theoretical study based on Density Functional Theory (DFT) and Time-Dependent (TD) DFT was conducted to optimize the geometrical structure and investigate the electronic properties of title compounds. The highest occupied molecular orbital (HOMO) was found on the benzothiazole moiety; while, the lowest-unoccupied molecular orbital (LUMO) was located at the benzoylthiourea fragment. The DFT optimized structures possessed an intramolecular hydrogen bonding and the types of para substituents used influenced the properties of hydrogen bonding.

 

Keywords: Benzothiazolyl-benzoylthiourea; DFT; electron donating groups; electron withdrawing groups; hydrogen bonding interactions

 

ABSTRAK

Kehadiran dua kromofor yang berbeza di dalam molekul benzotiazol iaitu benzotiazol dan gelang aromatik menyebabkan molekul ini mempunyai ciri kimia dan biologi yang menarik minat para penyelidik terhadap sebatian tersebut. Tiga sebatian benzotiazolil-benzoiltiourea yang baru dengan kumpulan pengganti daripada kumpulan penderma dan kumpulan penerima elektron (R) pada kedudukan para pada gelang benzoiltiourea iaitu 1-(1,3-benzotiazol-2-il)-3-(benzoiltiourea) (BBT), 1-(1,3-benzotiazol-2-il)-3-(4-klorobenzoiltiourea) (BBT-4Cl) dan 1-(1,3-benzotiazol-2-il)-3-(4-metoksibenzoiltiourea) (BBT-4OCH₃) berjaya disintesis daripada tindak balas R- benzoil isotiosianat (R = H, Cl dan OCH₃) dan 2-aminobenzotiazol. Sebatian tersebut telah diciri dengan teknik spektroskopi (inframerah, 1H proton RMN dan UV-Vis). Spektra inframerah sebatian menunjukkan frekuensi bagi jalurn (C=O), n (C=S), n (N-H) masing-masing pada 1664-1673, 1238-1249 dan 3031-3055 cm-1. Spektra 1H proton NMR menunjukkan kehadiran proton pada moieti N-H amina dan amida masing-masing pada 12.14-12.35 and 14.17-14.43 ppm. Kehadiran dua moieti benzotiazol dan benzoiltiourea ditunjukkan oleh isyarat proton pada julat 7.08-8.16 ppm. Kajian teori berdasarkan pengiraan dengan kaedah teori fungsi ketumpatan (DFT) dan DFT bersandar masa (TD) telah dijalankan untuk mengoptimumkan struktur geometri dan mengkaji sifat elektronik sebatian tersebut. orbital molekul terisi dengan tenaga tertinggi (HOMO) didapati pada moieti benzotiazol; manakala orbital molekul tidak terisi dengan tenaga terendah (LUMO) didapati pada moieti benzoiltiourea. Ikatan intramolekul hidrogen dapat dioptimumkan melalui DFT dan jenis kumpulan pengganti yang digunakan mempengaruhi sifat ikatan hidrogen tersebut.

 

Kata kunci: Benzotiazolil-benzoiltiourea; DFT; ikatan hidrogen; kumpulan penarik elektron; kumpulan penderma electron

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*Corresponding author; email: mb_kassim@ukm.edu.my