Synthesis, characterization and spectroscopic behavior of novel 2-oxo-1,4-disubstituted-1,2,5,6-tetrahydrobenzo[h]quinoline-3-carbonitrile dyes

Article abstract of DOI:10.1016/j.saa.2014.05.013

Two synthetic pathways were adopted to synthesize the target 2-oxo-1,4-disubstituted-1,2,5,6-tetrahydro-benzo[h]quinoline-3-carbonitriles. Structure of the synthesized compounds has been characterized based on FT-IR, ¹H NMR, ¹³C NMR

Full text of DOI:10.1016/j.saa.2014.05.013

Accepted Manuscript
Synthesis, characterization and spectroscopic behaviour of novel 2-oxo-1,4-
disubstituted-1,2,5,6-tetrahydrobenzo[h]quinoline-3-carbonitrile dyes
Salman A. Khan, Abdullah M. Asiri, Saad H. Al-Thaqafy, Hassan M. Faidallah,
Samy A. El-Daly
PII:
S1386-1425(14)00776-8
http://dx.doi.org/10.1016/j.saa.2014.05.013
SAA 12167
DOI:
Reference:
Spectrochimica Acta Part A: Molecular and Biomo-
lecular Spectroscopy
To appear in:
Received Date:
Revised Date:
Accepted Date:
19 February 2014
30 April 2014
9 May 2014
Please cite this article as: S.A. Khan, A.M. Asiri, S.H. Al-Thaqafy, H.M. Faidallah, S.A. El-Daly, Synthesis,
characterization
and
spectroscopic
behaviour
of
novel
2-oxo-1,4-disubstituted-1,2,5,6-
tetrahydrobenzo[h]quinoline-3-carbonitrile dyes, Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy (2014), doi: http://dx.doi.org/10.1016/j.saa.2014.05.013
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Synthesis, characterization and spectroscopic behaviour of novel
2-oxo-1,4-disubstituted-1,2,5,6-tetrahydrobenzo[h]quinoline-3-
carbonitrile dyes
Salman A Khana*, Abdullah M. Asiria,b, Saad H. Al-Thaqafya, Hassan M. Faidallaha, Samy A. El-
Dalya
a Department of Chemistry, Faculty of Science, King Abdulaziz University, P.O. Box 80203,
Jeddah 21589, Saudi Arabia
b Center of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz University,
P.O. Box 80203, Jeddah 21589, Saudi Arabia
* Corresponding author e-mail: sahmad_phd@Yahoo.co.in;Tel: no. 009660554953522
Abstract. Two synthetic pathways were adopted to synthesize the target 2-oxo-1,4-disubstituted-
1,2,5,6-tetrahydro-benzo[h]quinoline-3-carbonitriles. Structure of the synthesized compounds has
1
been characterized based on FT-IR, H-NMR, 13C-NMR and elemental analyses. UV-Vis and
fluorescence spectroscopy measurements provided that all compounds are good absorbent and
fluorescent. Fluorescence polarity study demonstrated that these compounds were sensitive to the
polarity of the microenvironment provided by different solvents. In addition, spectroscopic and
physicochemical parameters, including singlet absorption, extinction coefficient, Stokes shift,
oscillator strength and dipole moment were investigated in order to explore the analytical potential
of synthesized compounds.
Key words: Quinoline-3-carbonitrile; Fluorescence; Oscillator strength; Dipole moment
1

1. Introduction
Nitrogen containing heterocyclic compounds such as pyrazoline, pyrazole, pyimidines and
pyridines are important class of heterocyclic compounds due to their biological importance [1-3].
In recent years, pyridines and some derived fused ring systems such as quinolines and
tetrahydroquinolines have attracted much attention as versatile chemotherapeutic agents due to
their reported potential antimicrobial [4], antitubercular [5], antiamoebic [6], antiparasitic [7], and
antiviral [8] activities. As far as the chemotherapy of cancer is concerned, various fused pyridine
and quinoline compounds were reported to possess antineoplastic [9], cytotoxic [10],
antiproliferative [11], CDK kinase [12] and topoisomerase I, II inhibitory [13] activities.
Furthermore, particular interest has been given to cyanopyridine derivatives due to their well
documented anticancer and antiviral [14, 15] activities. Quniolines derivatives are also use as
ligands in the field of inorganic chemistry for the formation of metal complexes with Cu(II),
Ni(II), Co(II), Pt (II), Pd(II), Cd(II) and (Zn (II). On the other hand, quniolines derivatives are
widely used in materials science fields, such as, third order non-linear optics (NLO) [16], optical
switching [17], electrochemical sensing [18], Langmuir films and photoinitiated polymerization
[19]. Physicochemical characteristics, such as, solvatochromic, piezochromic, oscillator strength,
dipole moment, florescent quantum yield and photostability, are also the most important studies for
determining the behavior of compounds [20]. Several reactions were reported for the synthesis of
quinoline derivatives through ring annulations, intermolecular and intramolecular cyclization. All
these type reaction are multi steps reaction and low harsh reaction conditions and relatively overall
low yields. Due to wide range of applications of quinoline derivatives, we are reporting here the
synthesis of novel quinoline-3-carbonitrile by one-pot multi component reaction (MCR) with
higher yields and their physicochemical studies such as electronic absorption, molar absorptivity,
oscillator strength and dipole moment are also determine.
2

2. Results and Discussion
2.1. Chemistry
The synthetic strategies adopted for the preparation of the intermediate and target compounds
are described in Scheme 1. Two synthetic pathways were adopted to synthesize the target
tetrahydrobenzo[h]quinolines 4. The first method involved the formation of the 2-arylidene-
3,4-dihydro-2H-naphthalen-1-one 3 (chalcones) via Claisen-Schmidt condensation of the
appropriate aryl or heteroaryl aldehydes 2 with 3,4-dihydro-2H-naphthalene-1-one 1. These
chalcones 3a-f, in their turn, were allowed to react with ethyl cyanoacetate and ammonium
acetate to yield the target 2-oxo-1,4-disubstituted-1,2,5,6-tetrahydro-benzo[h]quinoline-3-
carbonitriles 4-9. On the other hand, the same compounds 4-9 could be directly prepared via
one-pot multicomponent reaction (MCR) of the 3,4-dihydro-2H-naphthalene-1-one 1, the
appropriate aldehyde 2, an excess of ammonium acetate and ethyl cyanoacetate in boiling
ethanol. Such type of reactions has received considerable interest since it is easier to perform,
gives higher yields and less time consuming. Therefore, a comparison of the data obtained
from the above-mentioned synthetic methods revealed that the one-pot reaction was better in
terms of yield percentage. The IR spectra of the tetrahydrobenzo[h]quinolines 4-9 exhibited
absorption bands at 2248-2218 cm-1 and 1678-1665cm-1 for the CN and CO groups,
1
respectively. Their structure was further confirmed from their H NMR which showed beside
the aromatic protons two multiplets at δ2.26-2.88 and 2.54 -2.90 ppm corresponding to the H-
5 and H-6 respectively.
2.2. Spectral behaviour of 3-Cyano-2-oxo-4-substituted-1,2,5,6-tetrahydrobenzo[h]quinolines
in different media
3

Absorption and emission spectra of 1 x10-5 mol dm-3 compounds (4-9) in various non-
polar, polar aprotic and protic solvents were studied (Fig 1a to Fig 6b). Calculated
physicochemical parameters obtained from steady state absorption and fluorescence spectra are
tabulated in Table 2-7. A close examination of Fig 1a-6a displays that the polarity of solvent has
a little effect on absorption maxima, indicating the weak polar character of compounds (4-9) in
the ground state. However, the emission spectra of these compounds are broad and red shifted as
the solvent polarity increases, as shown in Fig 1b-6b. The red-shift in chloroform to DMSO
indicates that photoinduced intramolecular charge transfer (ICT) occurring in the singlet excited
state from electron donating group to electron acceptor group [21]. As a result, the polarity of
compounds (4-9) increases on excitation.
2.3. Determination of oscillator strength and transition dipole moment
The solvatochromic behaviour in compounds (4-9) allows one to determine the difference
in the dipole moment between the excited singlet and the ground state (∆µ = µe – µg). This
difference can be obtained using the simplified Lippert- Mataga equation as follows [21, 22]:
2(µe − µg )2
∆ν st
=
∆f +Const.
(1)
(2)
hca3
D −1
n2 −1
∆f =
−
2D +1 2n2 +1
where ∆ν st is the Stokes–shift [23], which increases with increasing the solvent polarity pointing
to stronger stabilization of the excited state in polar solvents, h denotes Planck's constant, c refers
to the speed of light in vacuum and a is the Onsager cavity radius. Parameters D and n, in
equation 2, correspond to the dielectric constant and refractive index of the solvent, respectively.
The Onsager cavity radius was chosen to be 4.2 Å because this value is comparable to the radius
4

of a typical aromatic fluorophore [24]. Stokes shifts (∆νss ) of compounds (4-9) in different
solvents were calculated, as shown in Table 2-7, using the following the equation [21]:
∆νss =νex −νem
(3)
where νex and νe denote the wavenumbers of excitation and emission maxima (cm−1),
m
respectively. The change in dipole moment (∆µ) for compounds number 4, 5, 7 and 9 is negative
value which indicates that the ground state of these compounds is more polar than the singlet
excited state. For compounds 6 and 8 the ∆µ values are positive, indicating that the singlet exaited
is more polar than the ground state. The values of ∆µ are listed in Table. 8
The effective number of electrons transition from the ground to excited state is usually described
by the oscillator strength, which provides the absorption area in the electronic spectrum. The
oscillator strength, f, can be calculated using the following equation [25]:
f = 4.32×10−9 ε (ν ) dν
(4)
∫
where ε is the extinction coefficient (Lmol−1cm−1), and
represents the numerical value of
ν
wavenumber (cm−1). Oscillator strength values of compounds (4-9) in different solvents are
reported in Table 2-7. In addition, the transition dipole moment (µ) for compounds (4-9) from
ground to excited state in Debye was estimated in different solvents (Table 8) using the following
relation [26]:
f
µ 2 =
(5)
4.72 ×10−7 × Emax
where Emax is the maximum energy of absorption in cm-1
2.4. Fluorescence polarity study of compounds (4-9)
The steady state absorption and fluorescence parameters of 1 x 10-5M were recorded in
various polar aportic and polar protic solvents, as summarized in Table 2-7. The emission spectra
5

of compounds (4-9) are shown in Fig. 1b-6b. It can be clearly noted from Fig. 1b-6b that the
polarity of solvent has a significant effect on emission spectra, indicating the strong polar
character of all compounds in the ground state. The emission spectra, however, are broad and red
shifted as the solvent polarity increases from n-heptane to DMSO. The empirical Dimroth polarity
parameter, ET (30), was also calculated according to the following equation [27, 28].
28591
(6)
ET (solvent) =
λmax
where λmax corresponds to the peak wavelength (nm) in the red region of the intramolecular
charge transfer absorption of all compounds. The red (bathochromic) shift from n-heptane to
DMSO indicates that photoinduced intramolecular charge transfer (ICT) occurs in the singlet
excited state, and the polarity of compounds, therefore, increases on excitation.
In addition, the red shift of the compounds (4-9) fluorescence peak in alcoholic solvents
are assigned to solute–solvent hydrogen bonding interaction in the singlet excited state which
causes an extra red shift in the observed spectra.
3. Experimental
3.1. Chemicals and reagents
Appropriate aldehyde, 3,4-dihydro-2H-naphthalene-1-one and ethyl cyanoacetate were
purchased from Acros Organic. Other reagents and solvents (A.R.) were obtained commercially
and used without further purification, except dimethylformamide (DMF), ethanol and methanol.
Melting points were determined on a Gallenkamp melting point apparatus and are uncorrected.
The infrared (IR) spectra were recorded on Shimadzu FT-IR 8400S infrared spectrophotometer
using the KBr pellet technique. 1H and 13C NMR spectra were recorded on a Bruker DPX-600 FT
NMR spectrometer using tetramethylsilane as the internal standard and CDCl3 as a solvent
(Chemical shifts in δ, ppm). Splitting patterns were designated as follows: s: singlet; d: doublet;
6

m: multiplet; q: quartet. Elemental analyses were performed on a 2400 Perkin Elmer Series 2
analyzer and the found values were within 0.4% of the theoretical values. Follow up of the
reactions and checking the homogeneity of the compounds were made by TLC on silica gel-
protected aluminum sheets (Type 60 F254, Merck) and the spots were detected by exposure to
UV-lamp at λ 254. The chalcones 3a-f were prepared according to a reported procedure [29]. UV-
Vis electronic absorption spectra were acquired on a Shimadzu UV-1650 PC spectrophotometer.
Absorption spectra were collected using a 1 cm quartz cell. Steady state fluorescence spectra were
measured using Shimadzu RF 5301 PC spectrofluorphotometer with a rectangular quartz cell.
Emission spectra were monitored at right angle. All fluorescence spectra were blank subtracted
before proceeding in data analyses.
3.2. General method
Method A: A mixture of the appropriate chalcone 3 (10 mmol), ethyl cyanoacetate (1.1 g, 10
mmol) and ammonium acetate (6.2 g, 80 mmol) in absolute ethanol (30 m) was heated under
reflux for 8 h. After being cooled to room temperature, the solid product formed was filtered,
washed with water, dried and recrystallized from the DMF containing few drops of water
[30].
Method B: A one-pot mixture of the appropriate aldehyde 2 (10 mmol), 3,4-dihydro-2H-
naphthalene-1-one 1 (1.46 g, 10 mmol), ethyl cyanoacetate (1.1 g, 10 mmol) and ammonium
acetate (6.2 g, 80 mmol) in absolute ethanol (50 ml) was refluxed for 6 h. The reaction
mixture was allowed to cool, and the formed precipitate was filtered, washed with water,
dried and recrystallized [31]. Physicochemical and analytical data are listed in Table 1.
3.3. 4-(4-chlorophenyl)-2-oxo-1,2,5,6-tetrahydrobenzo[h]quinoline-3-carbonitrile (4):
7

1H NMR (CDCl3) ( /ppm): 8.24 (s, NH), 7.03-7.28 (m, CH,aromatic, 8H), 2.27 (m, CH2cyclo, H-
13
5 , 2H), 2.56 (m, CH2cyclo, H-6 , 2H), CNMR (CDCl3) : 29.8 (C-5), 29.7 (C-6), 117.1 (CN),
95.5, 114.2 128.5, 162.8 (CO), 169.3, (pyridine C), 125.4, 126.1, 126.3, 127.4, 127.6 127.7,
128.4, 134.2, 134.7, 137.9 (Ar C). Anal. calc. for C20H13ClN2O: C, 72.18, H, 3.94, N, 8.42; Found:
C, 72.22, H, 4.01, N, 8.45.
3.4. 4-(4-nitrophenyl)-2-oxo-1,2,5,6-tetrahydrobenzo[h]quinoline-3-carbonitrile (5):
1H NMR (CDCl3) ( /ppm): 8.15 (s, NH), 7.04-8.12 (m, CH,aromatic, 8H), 2.27 (m, CH2cyclo, H-
13
5 , 2H), 2.74 (m, CH2cyclo, H-6 , 2H), CNMR (CDCl3) : 29.5 (C-5), 29.4 (C-6), 117.8
(CN),95.2,114.5,128.2,162.9(CO),169.2,(pyridineC),114.0,120.5,120.7,125.6,126.2,
127.2,
127.6,127.8,128.7,134.4,137.9,159.7(Ar C); Anal. calc. for C20H13N2O3: C, 69.96, H, 3.82, N,
12.24; Found: C, 70.10, H, 3.86, N, 12.29.
3.5. 4-(4-hydroxy-2-methoxyphenyl)-2-oxo-1,2,5,6-tetrahydrobenzo[h]quinoline-3-carbonitrile
(6): 1H NMR (CDCl3) ( /ppm): 8.25(s, NH), 6.55-7.04 (m, CH,aromatic, 7H), 2.29 (m, CH2cyclo,
13
H-5 , 2H), 2.60 (m, CH2cyclo, H-6 , 2H), 5.73 (s, OH), 3.73 (s, O-CH3, 3H); CNMR (CDCl3) :
29.8 (C-6), 29.7 (C-7), 92.2 (CH2), 117.9 (CN), 96.2, 114.1, 128.2, 160.8(CO), 169.9(pyridine C),
113.2,116.3,119.9,125.2.126.3,127.5,127.7,128.5,134.2,137.9,142.1,149.0(Ar C).; Anal. calc. for
C20H13N2O3: C, 69.96, H, 3.82, N, 12.24; Found: C, 70.10, H, 3.86, N, 12.29.
3.6. 4-(furan-3-yl)-2-oxo-1,2,5,6-tetrahydrobenzo[h]quinoline-3-carbonitrile (7)
1H NMR (CDCl3) ( /ppm): 8.30(s, NH), 6.65-7.00(m, CH,aromatic, 7H), 2.26 (m, CH2cyclo, H-5
13
, 2H), 2.65 (m, CH2cyclo, H-6 , 2H); CNMR (CDCl3) : 29.8 (C-6), 29.7 (C-7), 92.2 (CH2),
117.9 (CN), 96.2, 114.1, 128.2, 160.8(CO), 169.9 (pyridine C),113.2, 116.3, 119.9, 125.2,
126.3,127.5,127.7,128.5,134.2,137.9,142.1,149.0(Ar C).; Anal. calc. for C18H12N2O2: C, 74.99, H,
4.20, N, 9.72; Found: C, 75.01, H, 4.25, N, 9.76.
3.7. 4-[4-(dimethylamino)phenyl]-2-oxo-1,2,5,6-tetrahydrobenzo[h]quinoline-3-carbonitrile (8)
8

1H NMR (CDCl3) ( /ppm): 8.13(s, NH), 6.56-7.28 (m, CH,aromatic, 8H), 2.28 (m, CH2cyclo, H-5
, 2H), 2.59 (m, CH cyclo, H-6 , 2H), 2.89 (s, N(CH ) , 6H); 13CNMR (CDCl ) : 43.6 (NCH3)29.9
2
3
2
3
(C-6), 30.0 (C-5), 96.8, 112.8, 114.6, 115.3, 117.6 (CN), 113.0, 114.4, 125.4, 126.2, 127.1, 127.6,
127.8, 134.1, 137.8, 143.6 (Ar C), 95.8, 114.1, 128.7, 162.8 (CO),169.4 (pyridine C); Anal. calc.
for C22H19N3O: C, 77.40, H, 5.61, N, 12.31; Found: C, 77.52, H, 5.73, N, 12.37.
3.8. 4-(2-methoxyphenyl)-2-oxo-1,2,5,6-tetrahydrobenzo[h]quinoline-3-carbonitrile (9):
1H NMR (CDCl3) ( /ppm): 8.24 (s, NH), 6.72-7.03 (m, CH,aromatic, 8H), 2.29 (m, CH2cyclo, H-
13
5 , 2H), 2.62 (m, CH2cyclo, H-6 , 2H), 3.72 (s, O-CH3, 3H); CNMR (CDCl3) 29.9 (C-5), 29.6
(C-6), 56.4 (CH3O), 117.2 (CN), 96.1, 114.1, 128.9, 162.9(CO), 169.2 (pyridine C), 123.3, 125.2,
126.1, 127.6, 127.7, 128.6, 131.7, 134.2, 134.8, 141.2 (Ar C); Anal. calc. for C21H16N2O2: C,
76.81, H, 4.91, N, 8.53; Found: C, 76.76, H, 4.88, N, 8.48.
4. Conclusion
Two synthetic pathways were adopted to synthesize the target 2-oxo-1,4-disubstituted-1,2,5,6-
tetrahydro-benzo[h]quinoline-3-carbonitriles. The first method involved the formation of the
chalcones via Claisen-Schmidt condensation. These chalcones react with ethyl cyanoacetate and
ammonium acetate to
yield
the target
2-oxo-1,4-disubstituted-1,2,5,6-tetrahydro
benzo[h]quinoline-3-carbonitriles 4-9. On the other hand, the same compounds 4-9 could be
directly prepared via one-pot multicomponent reaction (MCR). Such type of reactions has
received considerable interest since it is easier to perform, gives higher yields and less time
consuming. Therefore, a comparison of the data obtained from the above-mentioned synthetic
methods revealed that the one-pot reaction was better in terms of yield percentage.
Physicochemical studies of the compounds including singlet absorption, extinction coefficient,
9

Stokes shift, oscillator strength and dipole moment were investigated on the basis of the polarity
of solvent.
Acknowledgments
The authors are thankful to the Chemistry Department at King Abdulaziz University for providing
research facilities.
References
[1].S. A. Khan, A. M. Asiri, J. Hetrocycl. Chem., 49 (2012) 1434-1438.
[2].A. M. Asiri, S. A. Khan,. Molecules, 16 (2011) 523-531
[3].S. A. Khan, A. M. Asiri, S. Kumar, K. Sharma, Eur. J. Chem., 5 (1) (2014) 85‐90.
[4].S. A. Khan, A. M. Asiri, K. Sharma, Med. Chem. Res., 22 (2013) 1998-2004.
[5].M. V. N. Souza, K. C. Pais, C. R. Kaiser, M. A. L. Peralta, M. L. Ferreira, M. C. S. Lourenço,
Bioorg. Med. Chem., 17 (2009) 1474-1480.
[6].F. Hayat, A. Salahuddin, S. Umar, A. Azam, Eur. J. Med. Chem., 45 (2010) 4669-4675.
[7].A. M. Asiri, A. O. Baglaf, R. M. Abdel-Rahman, S. A. Khan, M. Ishaq, Asian J. Chem., 25
(2013) 7779-7782.
[8].L. M. Bedoya, M. J. Abad, E. Calonge, L. A. Saavedra, C. M. Gutierrez, V. V. Kouznetsov, J.
Alcami, P. Bermejo, Anti Rese., 87 (2010) 338-344.
[9].M. G. Ferlin, B. Gatto, G. Chiarelotto, M. Palumbo, Bioorg. Med. Chem., 8 (2000) 1415-
1422.
[10]. N. Chowdhury, M. Gangopadhyay, S. Karthik, N. D. P. Singh, M. Baidya, S. K. Ghosh, J.
Phto. Chem. Phto Biol B: 130 (2014) 188-198.
[11]. R. K. Arafa, G. H. Hegazy, G. A. Piazza, A. H. Abadi, Eur. J. Med. Chem., 63 (2013)
826-832.
10

[12]. F. Sliman, M. Blairvacq, E. Durieu, L. Meijer, J. Rodrigo, D. Desmaele, Bioorg. Med.
Chem. Lett., 20 (2010) 2801-2805.
[13]. A. Cagir, B. M. Eisenhauer, R. Gao, S. J. Thomas, S. M. Hecht, Bioorg. Med. Chem., 12
(2004) 6287-6299.
[14]. N. Kumar, A. Chauhan, S. Drabu, Biomed. Pharma., 65 (2011) 375-380.
[15]. S. Khaksar, M. Yaghoobi, M., J. Flu. Chem., 152 (2012) 41-44.
[16]. J. C. Calabrese, W. Tam, Chem. Phy. Lett., 133 (1987) 244-245.
[17]. E. Inkaya, S. Gunnaz, N. Ozdemir, O. Dayan, M. Dinçer, B. Cetinkaya, Sepctrochim. Acta
Part A: 103 (2013) 255-263.
[18]. T. K. Khan, M. Ravikanth, Dyes & Pigments, 95 (2012) 89-95.
[19]. P. Hao, Y. Chen, T. Xiao, W. Sun, J. Organometalic Chem., 95 (2010) 90-95.
[20].
(2012) 1900-1906.
[21]. A. M. Asiri, S. A. El-Daly, S. A. Khan, Spectrochim Acta, Part A: 95 (2012) 679-684.
A. M. Asiri, S. A. Khan, M. S. Al-Amodi, K. A. Alamry, Bull. Kore Chem Soci., 33
[22].
A. M. Asiri, H. M. Marwani, S. A. Khan, K. Sharma, J. Pohtochem. Photobiol., A 120
(2013) 82-89.
[23].
(1994) 2537-2544.
W. E. Acree, D. C. Wilkins, S. A. Tucker, J. M. Griffin, J. R. Powell, J. Phys. Chem. 98
[24]. S. Kumar, V. C. Rao, R. C. Rastogi, , Spectrochim. Acta A. 57 (2001) 41-47.
[25]. N. J. Turro, Molecular photochemistry (frontiers in chemestry), 1st ed., W. A. Benjamin,
Inc., Reading, MA, (1965) 286.
11

[26]. B. J. Coe, J. A. Harris, I. Asselberghs, K. Clays, G. Olbrechts, A. Persoons, J. T. Hupp,
R. C. Johnson, S. J. Coles, M. B. Hursthouse, K. Adv. Funct. Mater. 12 (2002) 110-116.
[27]. M. Ravi, A. Samanta, T. P. Radhakrishnan, J. Phys. Chem. 98 (1994) 9133-9136.
[28]. M. Ravi, T. Soujanya, A. Samanta, T. P. Radhakrishnan, J. Chem. Soc. Faraday Trans.
91 (1995) 2739- 2742.
[29]. S. A. Khan, A. M. Asiri, S. Kumar, K. Sharma, Eur. J. Chem., 5 (2014) 85-90.
[30]. H. M. Faidallah , K. A.Khan, A. M. Asiri, J. Chem. Sci., 124 (2012) 25–631.
[31]. H. M. Faidallah , S.A.F. Rostom, Eur. J. Med. Chem., 63 (2013) 133-143.
12

O
O
+
H
R
2a-f
1
iii
i
R
O
CN
O
ii
R
N
H
3a-f
4-9
Scheme 1. Reagents and reaction conditions: (i) potassium hydroxide, ethanol, r.t., 6-8h;
(ii) ethyl cyanoacetate, ammonium acetate, ethanol, reflux, 6-8h; (iii) (one-put) ethyl cyanoacetate, ammonium
acetate, ethanol, reflux, 3-6h.
13

Table 1. Physicochemical data of the synthesized compounds (4-9).
o
Crystallization % Yield m.p C
Compound
no.
Molecular
formula
R
A/B
C20H13ClN2O2
>360
4
5
CHCl3
70/88
Cl
>360
C20H13N3O3
CH3OH:CHCl3 75/90
C2H5OH:CHCl3 76/92
CH3OH:CHCl3 75/87
O2N
C21H16N2O3
320-322
6
HO
OMe
C18H12N2O2
285-87
>360
7
8
O
C22H12N2O2
CHCl3
75/87
N
14

9
C21H16N2O2
CH3OH:CH2Cl2 72/86
250-52
OMe
Table 2. Spectral data of compound no. 4 in different solvents.
µ
ET (30)
∆ν
ε
∆f
λab(nm) λem(nm)
Debye
Solvent
f
Kcal
M -1cm-1
(cm-1)
mol-1
EtOH
0.288 72.38
0.308 72.56
0.263 70.94
0.275 71.29
0.188 71.83
0.304 72.01
0.021 71.29
0.0004 72.19
395
394
403
401
398
397
401
396
488
447
459
456
451
453
456
449
8970
11150
9000
7680
11400
10610
5700
2950
0.10
0.13
0.09
0.09
0.13
0.13
0.06
0.03
2.99
2.34
2.81
2.80
3.36
3.33
2.40
1.71
2995
3009
2591
3008
2953
3113
3008
2981
MeOH
DMSO
DMF
CHCl3
CH3CN
Dioxan
n-Heptane
15

Table 3. Spectral data of compound no. 5 in different solvents.
µ
ET (30)
∆ν
ε
∆f
λab(nm) λem(nm)
Debye
Solvent
f
Kcal
M -1cm-1
(cm-1)
mol-1
EtOH
0.288 72.56
0.308 72.56
0.263 70.42
0.275 70.94
0.188 71.12
0.304 71.65
0.021 71.29
394
394
406
403
402
399
401
452
448
449
453
458
454
463
11630
13010
11240
11240
13110
13680
11910
0.15
0.16
0.10
0.12
0.15
0.16
0.15
3.53
3.75
3.01
3.26
3.67
3.74
3.67
3257
3059
2359
2798
3041
3036
3339
MeOH
DMSO
DMF
CHCl3
CH3CN
Dioxan
Table 4. Spectral data of compound no. 6 in different solvents.
µ
ET (30)
∆ν
ε
∆f
λab(nm) λem(nm)
Debye
Solvent
f
Kcal
M -1cm-1
(cm-1)
mol-1
EtOH
MeOH
DMSO
DMF
0.288 73.31
0.308 73.31
0.263 71.83
0.275 72.38
0.188 72.38
0.304 72.38
0.021 72.38
390
390
398
395
395
395
399
394
455
448
459
461
457
459
457
452
9000
9070
17200
15800
12740
9330
6680
3590
0.13
0.12
0.23
0.22
0.18
0.131
0.08
0.04
3.2
3663
3320
3466
3561
3371
3530
3181
3257
3.1
4.4
4.2
CHCl3
CH3CN
Dioxan
3.88
3.31
2.66
1.92
n-Heptane 0.004 72.56
16

Table 5. Spectral data of compound no. 7 in different solvents.
µ
ET (30)
∆ν
ε
∆f
λab(nm) λem(nm)
Debye
Solvent
f
Kcal
M -1cm-1
(cm-1)
mol-1
EtOH
0.288 72.75
0.308 72.75
0.263 68.90
0.275 71.12
0.188 71.65
0.304 71.65
0.021 71.29
393
393
409
402
399
399
401
386
462
462
466
463
465
463
468
459
15100
16900
13000
12300
15700
13700
7680
0.22
0.25
0.15
0.16
0.22
0.18
0.10
0.17
4.27
4.56
3.66
3.70
4.31
3.90
2.90
3.72
3800
3800
2990
3277
3557
3464
3570
4120
MeOH
DMSO
DMF
CHCl3
CH3CN
Dioxan
n-Heptane 0.004 74.06
10640
Table 6. Spectral data of compound no. 8 in different solvents.
µ
ET (30)
∆ν
ε
∆f
λab(nm) λem(nm)
Debye
Solvent
f
Kcal
M -1cm-1
(cm-1)
mol-1
EtOH
0.288 68.23
0.308 68.39
0.263 66.64
419
418
429
426
422
417
416
406
458
465
467
466
432
467
468
441
23800
23130
24100
22600
26350
25210
22010
20400
0.19
0.22
0.18
0.18
0.51
0.25
0.23
0.35
4.13
4.44
4.06
4.05
6.79
4.77
4.55
5.49
3663
3320
3466
3561
3371
3530
3181
3257
MeOH
DMSO
DMF
0275
67.11
CHCl3
CH3CN
Dioxan
0.188 67.22
0.304 60.70
0.021 68.72
n-Heptane 0.004 70.42
17

Table 7. Spectral data of compound no. 9 in different solvents.
µ
ET (30)
∆ν
ε
∆f
λab(nm) λem(nm)
Debye
Solvent
f
Kcal
M -1cm-1
(cm-1)
mol-1
EtOH
MeOH
DMSO
DMF
0.288 73.31
0.308 73.31
0.263 72.01
0.275 72.56
0.188 72.75
0.304 72.56
0.021 72.01
390
390
397
394
393
394
397
383
451
452
457
453
452
450
456
442
9640
11180
9224
8620
11210
10800
8390
9180
0.13
0.15
0.12
0.11
0.14
0.13
0.10
0.12
3.31
3.60
3.20
3.07
3.51
3.36
3.02
3.21
3469
3517
3307
3305
3321
3158
3259
3485
CHCl3
CH3CN
Dioxan
n-Heptane 0.004 74.65
18

Table 8. Change in ∆µ of compounds (4-9)
Compound no
∆µ (Debye)
4
5
6
7
8
9
-0.72
-3.05
2.72
-2.97
0.06
-0.70
19

0.12
0.10
0.08
0.06
0.04
0.02
0.00
EtOH
MeOH
DMSO
DMF
CHCl
3
Acetonitrile
Dioxan
n-Heptane
325
350 375
Wavelength (nm)
400
425
450
Fig. 1a- Electronic absorption spectra of 1 × 10-5 mol dm-3 of compound 4 in different solvents.
20

0.15
0.12
0.09
0.06
0.03
0.00
EtOH
MeOH
DMSO
DMF
CHCl3
Acetonitrile
Dioxan
350
400
450
500
Wavelength (nm)
Fig. 2a- Electronic absorption spectra of 1 × 10-5 mol dm-3 of compound 5 in different solvents
21

EtOH
MeOH
DMSO
DMF
0.24
0.21
0.18
0.15
0.12
0.09
0.06
0.03
0.00
CHCl
3
Acetonitrile
Dioxan
n-Heptane
300
350
400
450
Wavelength (nm)
Fig. 3a- Electronic absorption spectra of 1 × 10-5 mol dm-3 of compound 6 in different solvents
22

0.18
0.15
0.12
0.09
0.06
0.03
0.00
EtOH
MeOH
DMSO
DMF
CHCl
3
Acetonitrile
Dioxan
n-Heptane
350
400
450
500
Wavelength (nm)
Fig. 4a- Electronic absorption spectra of 1 × 10-5 mol dm-3 of compound 7 in different solvents
23

0.30
0.25
0.20
0.15
0.10
0.05
0.00
EtOH
MeOH
DMSO
DMF
CHCl
3
Acetonitrile
Dioxan
n-Heptane
350
400
450
500
Wavelength (nm)
Fig. 5a- Electronic absorption spectra of 1 × 10-5 mol dm-3 of compound 8 in different solvents
24

0.12
0.10
0.08
0.06
0.04
0.02
0.00
EtOH
MeOH
DMSO
DMF
CHCl3
Acetonitrile
Dioxan
n-Heptane
350
400
450
Wavelength (nm)
Fig. 6a- Electronic absorption spectra of 1 × 10-5 mol dm-3 of compound 9 in different solvents.
25

900
800
700
600
500
400
300
200
100
0
EtOH
MeOH
DMSO
DMF
CHCl
3
Acetonitrile
Dioxan
n-Heptane
400
450
500
Wavelength (nm)
550
600
Fig. 1b- Emission spectra of 1 × 10-5 mol dm-3 of compound 4 in different solvents.
26

700
600
500
400
300
200
100
0
EtOH
MeOH
DMSO
DMF
CHCl
3
Avetonitrile
Dioxan
400
450
500
Wavelength (nm)
550
600
Fig. 2b- Emission spectra of 1 × 10-5 mol dm-3 of compound 5 in different solvents.
27

800
700
600
500
400
300
200
100
0
EtOH
MeOH
DMSO
DMF
CHCl
3
Acetonitrile
Dioxane
n-Heptane
400
450
500
550
600
Wavelength (nm)
Fig. 3b- Emission spectra of 1 × 10-5 mol dm-3 of compound 6 in different solvents.
28

450
400
350
300
250
200
150
100
50
EtOH
MeOH
DMSO
DMF
CHCl
3
Acetonitrile
Dioxan
n-Heptane
0
400
450
500
550
600
Wavelength (nm)
Fig. 4b- Emission spectra of 1 × 10-5 mol dm-3 of compound 7 in different solvents.
29