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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. KASSIM1,2*
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
Diserahkan: 20
September 2017/Diterima: 29 Disember 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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*Pengarang untuk surat-menyurat; email: mb_kassim@ukm.edu.my
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