untitled


ISSN	215

Synthes
based	o

Naglaa	Sa

1	Department	of
2	Department	of

*	Corresponding
Tel.:	+2.097.247

	
	

	

ARTICLE	IN

DOI:	10.5155/e

Received:	12	Se
Received	in	rev
Accepted:	29	No
Published	onlin
Printed:	31	Mar

KEYWORDS
Absorption	
Merocyanine	
Metal	complex	
Photosensitizat
Antimicrobial	a
Bis‐coumarin‐β

	
1.	Introduct
	

Coumari
organic	 lumi
radiation	 in
polymethine
promising	 p
Psoralens	 (f
logy	and	pho
that	form	str
and	 proteins
biochemistry
Fluorescent	
exhibit	 excel
cent	coumar
fish	 retinal	c
been	 shown
antithrombo
tics	 [20],	 an
antibacterial
coumarins	 a
our	work	in	
new	 cyanin

53‐2249	(Print)	

	

	

	

sis,	spectr
n	bis‐cou

lah	El‐Deen	

f	Chemistry,	Faculty
f	Chemistry,	Faculty

g	author	at:	Depart
71479.	Fax:	+2.07.4

FORMATION	

	
eurjchem.7.1.66‐72

eptember	2015	
vised	form:	29	Octo
ovember	2015	
ne:	31	March	2016	
rch	2016	

S	

tion	
activity	
β‐dicarbonyl	

tion	

n	 derivatives	
inophores	and	
n	 the	 region	
es	 have	 efficien
probes	 in	 bi
furocoumarins)
oto	chemothera
rongly	fluoresce
s	 have	 found	 b
y	for	identificat
characteristic

llent	 performa
rin	derivatives	w
cell	 [16].	Coum
n	 to	 possess	 m
otic	 [17],	 antim
nti‐inflammator
l	 [24],	 anti‐HIV
are	 used	 as	 ant
the	field	of	cya
ne	 dyes	 have	

/	ISSN	2153‐225
ht

Europ

roscopic	a
marin	het

	Mohamed	1

y	of	Science	and	Ar
y	of	Science,	Aswan

tment	of	Chemistry,
80450.	E‐mail	addr

2.1319	

ober	2015	

constitute	 an	
laser	dyes	 that
of	 400‐560	 n
nt	 fluorescenc
ochemistry	 an
)	 became	 impo
apy	[8‐10].	Cur
enting	complex
broad	 applicatio
tion	of	bio	mac
cs	 of	 coumar
nce	 as	 sensitiz
were	used	in	v

marins	and	relat
many	 biologica
microbials	 [18,1
ry	 [21,22],	 an
V	 [25],	 antifung
tioxidants	 [27‐2
anine	dyes,	in	th
been	 prepar

European	Journ

Europ
57	(Online)		20
ttp://dx.doi.org

pean	Jo
Journal	web

and	antim
terocycle

1,2,*	and	Rag

ts,	Najran	Universi
n	University,	Aswan

y,	Faculty	of	Science
ress:	naglaanaglaa

	 	

	 	

	 ABSTRACT
	 Novel	 symm
monomethine
mono‐5[2(4)]
compound	de
oxo1,3‐bis(2‐o
complexes.	 St
basis	 of	 elem
relationship	o
of	 photosensi
which	 investi
have	been	inv
sp.	

Cite	this:	Eur.

important	 gro
t	efficiently	gen
nm	 [1‐3].	 Cou
e	 that	 makes	
nd	 medicine	
ortant	 for	 pho
rrently,	 cyanine
xes	with	nucleic
on	 in	 chemistr
romolecules	[1
rin	 photosensi
zer	 [13‐15].	 Flu
vivo	imaging	of	
ted	compounds
al	 activities	 su
19],	 chemother
ti‐proliferative	
gal	 [26]	 and	ma
29].	 An	 extens
his	manuscript,
red	 from	 cou

al	of	Chemistry	7

	

pean	Journal	of	C
016	Atlanta	Pub
/10.5155/eurjch

	

ournal	
bpage:	www.

	

microbial	s
es	derivati

ab	Mohame

ity,	Najran,	11114,	K
,	81528,	Egypt	

e	and	Arts,	Najran	U
a@yahoo.com	(N.S.E

metrical	 and	
e	like,	pentameth
]‐methine	cyanin
erivatives	named
oxo‐2H‐chromen
tructure	 determ
mental	 analysis
of	new	dyes	have
itizing	 effect	 thr
igated	 in	 95%	e
vestigated	agains

.	J.	Chem.	2016,	

oup	 of	
nerate	
marin	
them	
[4‐7].	
tobio‐
e	dyes	
c	acids	
ry	 and	
11,12].	
itizers	
uores‐
zebra	
s	have	
uch	 as	
rapeu‐
[23],	

any	of	
ion	 of	
	some	
marin	

der
field
	
2.	E
	
2.1.
	

carr
The
Infr
spe
usin
shif
wer
Uni
with
reco
 

2.2.
	
2.2.
	

[30

7	(1)	(2016)	66‐

Chemistry	
lishing	House	LL
hem.7.1.66‐72.1

of	Che
.eurjchem.co

studies	of
ives	

d	AbuEl‐Ha

Kingdom	Saudi	Ara

University,	Najran,	
E.	Mohamed).	

unsymmetrical	
hine	cyanine,	mo
ne	dye	have	bee
d	as	1,3‐bis‐(2‐o
n‐3‐yl)prop‐1‐en
mination	 of	 the	 n
,	 IR,	 1H	 NMR	
e	been	discussed
rough	 the	UV	 vi
ethanol.	Antimic
st	Streptococcus

7(1),	66‐72	

rivatives	of	high
d	applications.

Experimental

.	Instrumentat

All	melting	poi
ried	 out	 at	 the
e	 IR	 spectra	 (K
rared	 127	 spec
ectra	 were	 reco
ng	tetra	methyl
fts	are	reported
re	 recorded	 o
iversity).	The	 e
hin	the	wavele
ording	spectrop

.	Synthesis	

.1.	Synthesis	of

The	 compound
].	

‐72	

LC	‐	All	rights	re
1319	

emistry
m	

f	some	no

md	2	

abia	

11114,	Kingdom	S

cyanine	 dye
onomethine‐me
n	prepared	thro
oxo‐2H‐chromen
nyloxy)	 copper,
new	 compound
and	 MS	 spect

d	on	the	basis	of	
isible‐absorption
robial	 propertie
s	sp,	Staphylococc

h‐sensitivity	and

tions	

ints	are	uncorr
	Micro	Analyti
KBr)	 were	 det
ctrophotometer
orded	 with	 Bru
l	silane	(TMS)	a
d	as	δ	in	parts	p
on	 an	 HpMs	
electronic	 absor
ngth	range	350
photometer,	Fa

f	3‐acetylchrom

d	1	was	 carrie

served	‐	Printed

y	

vel	cyanin

audi	Arabia.		

es,	 incorporatin
so‐substituted‐p
ough	the	synthes
n‐3‐yl)	propane‐
	 cobalt	 and	 nic
s	 has	 been	 char
ra.	 Structure	 p
their	spectral	be
n	 spectra	 of	 all	
es	 of	 some	 selec
cus	sp,	Salmonel

d	high‐wavelen

rected.	Element
cal	 Center	 (Cai
termined	 with	
r	 (Cairo	 Univer
uker	 AMX‐500
as	internal	refer
per	million	(pp
6988	 spectro

rption	spectra	
0‐800	nm	on	64
aculty	of	Science

men‐2‐one	(1)	

ed	 out	 accordin

d	in	the	USA	

	

	

	

ne	dyes	

ng	 merocyanin
pentamethine	an
sis	of	new	startin
1,3‐dione	and	(
ckel	 chloride	 sa
racterized	 on	 th
photosensitizatio
ehavior	as	criter
synthesized	 dy
cted	 cyanine	dy
lla	sp.	and	Shigel

ngth	with	wide‐

tal	analysis	was
iro	University).
Perkin	 Elmer
rsity).	 1H	 NMR
	 spectrometer,
rence.	Chemical
m).	MS	spectra
ometer	 (Cairo
were	 recorded
405	UV/Visible
e,	Aswan.	 

ng	 to	 reference

ne
nd
ng
3‐
alt
he
on
ria
es
es
lla

‐

s	
.	
r	
R	
,	
l	
a	
o	
d	
e	

e	



Mohamed	and	AbuEl‐Hamd	/	European	Journal	of	Chemistry	7	(1)	(2016)	66‐72	 67	
 

	

I2

N
O

O O

O O

O O OOEtOH/pip

N O

O

O O

O

O

A

I2

N

N

O O

O

O

O

O

I-

EtOH/pip

A
A' I-

N NR'R

O O

O

OH

EtOH/pip

A''

N

6a-c

I-

MCl2 / EtOH

O O

O O OO

M Cl-

+

M

O O

O O OO
CH

N

A

EtOH/pip

9a-c

10a-e

NaOH / EtOH

O

O O

N
I-

N
I-

+
AH3C

N
I-

AH3C

+
Cl-

N
I-

AH3C

N
I-

A

+

+
N

N

CH

N R R'

8a- c

+

+

1 2 3

4

2M

+

3M

7

5a-c

+

I- AA'

 
 
5a‐c:	N‐Ethyl	pyridine	(a),	N‐ethylquinoline	(b),	N‐ethyl	isoquinoline	(c);	6a‐c:	A=	Pyridin‐2‐ium	ethyl	iodide,	A'=	N‐ethyl	pyridine,	R=	R'=	2‐oxo‐2H‐chromen‐
3‐yl	(a)	A=	Quinolin‐2‐ium	ethyl	iodide,	A'=	N‐ethylquinoline,	R=	R'=	2‐oxo‐2H‐chromen‐3‐yl	(b)	A=	Pyridine‐4‐ium	ethyl	iodide,	A'=	N‐ethyl	pyridine,	R=	R'=	2‐
oxo‐2H‐chromen‐3‐yl	 (c);	8a‐c:	A=	Pyridin‐2‐ium	ethyl	 iodide,	A'=A''=	N‐ethyl	 pyridine,	R=	R'=	2‐oxo‐2H‐chromen‐3‐yl	 (a)	A=	Quinolin‐2‐ium	ethyl	 iodide,	
A'=A''=	N‐ethylquinoline,	R=	R'=	2‐oxo‐2H‐chromen‐3‐yl	(b)	A=	Pyridine‐4‐ium	ethyl	iodide,	A'=	A''=N‐ethyl	pyridine,	R=	R'=	2‐oxo‐2H‐chromen‐3‐yl	(c);	9a‐c:	
M=	Cu2+	(a),	M=	Co2+	(b),	M=	Ni2+	(c);	10a‐e:	M=	Cu2+,	A=	N‐ethyl	pyridine	(a),	M=	Cu2+,	A=	N‐ethylquinoline	(b)	M=	Cu2+,	A=	N‐ethyl	pyridine	(c),	M=	Co2+,	A=	N‐
ethylquinoline	(d)	M=	Ni2+,	A=	N‐ethylquinoline	(e)	
 

Scheme	1
	
	
2.2.2.	Synthesis	of	1‐(2‐oxo‐2H‐chromene‐3‐carbonyl)	
pyridinium	iodide	(2)	
	

The	 compound	2	 was	 carried	 out	 according	 to	 reference	
[31].	A	mixture	of	 compound	1	 (0.01	mol),	 iodine	 (0.01	mol)	
and	pyridine	 (50	mL)	was	 refluxed	 for	 1	 h,	 on	 a	water	 bath,	
filtered	 hot,	 concentrated	 and	 cooled.	 The	 precipitated	
products	 after	dilution	with	50	mL	water	were	 collected	and	
crystallized	 from	 aqueous	 ethanol	 to	 give	 the	 corresponding	
compound	2	(Scheme	1).	Color:	White.	Yield:	83%.	M.p.:	196‐
198	°C.	Anal.	 calcd.	For	C15H10O3NI:	C,	47.52;	H,	2.66;	N,	3.69.	
Found:	C,	47.53;	H,	2.75;	N,	3.71%.	

	
2.2.3.	Synthesis	of	2‐oxo‐2H‐chromene‐3‐carboxylic	acid	(3)	
	

The	 compound	2	 (0.01	mol)	was	dissolved	 in	 ethanol	 30	
mL	 in	 presence	 of	 sodium	 hydroxide	 (0.5	 mL	 of	 10%).	
Reaction	mixture	was	refluxed	for	3	h,	filtered	hot,	cooled	and	
neutralized	 with	 conc.	 hydrochloric	 acid	 0.5	 mL.	 The	
precipitated	product	 after	dilution	with	water	were	 collected	
and	 crystallized	 from	 ethanol	 to	 give	 the	 corresponding	
compound	3	 (Scheme	1).	Color:	Green	colored	powder.	Yield:	
65%.	M.p.:	195‐197	°C.	FT‐IR	(KBr,	ν,	cm‐1):	3300	(ν	OH),	2920	
(ν	CH),	1719	(Lactone),	1680	(ν	CO).	Anal.	calcd.	for	C10H6O4:	C,	
63.16;	H,	3.18.	Found:	C,	63.01;	H,	3.30%.	



68	 Mohamed	and	AbuEl‐Hamd	/	European	Journal	of	Chemistry	7	(1)	(2016)	66‐72	
	
2.2.4.	Synthesis	of	1,3‐bis(2‐oxo‐2H‐chromen‐3‐yl)propane‐
1,3‐dione	(4)	
	

Mixture	of	compound	3	(0.01	mol)	with	compound	1	(0.01	
mol)	and	piperidine	0.7	mL	was	fused	for	1	h,	on	water	bath.	
The	 reaction	 mixture	 was	 dissolved	 in	 30	 mL	 ethanol	 and	
refluxed	for	3	h,	cooled	to	room	temperature	and	poured	into	
50	 mL	 ice‐water.	 The	 precipitated	 solid	 were	 collected	 and	
crystallized	from	ethanol	to	give	the	corresponding	compound	
4	(Scheme	1).	Color:	Deep	green	colored	powder.	Yield:	70%.	
M.p.:	 145‐147	 °C.	 FT‐IR	 (KBr,	 ν,	 cm‐1):	 2922	 (C‐H),	 1722	
(Lactone),	1608	(CO).	1H	NMR	(500	MHz,	CDCl3,	δ,	ppm):	7.30‐
8.85	(m,	8H,	Ar	H),	8.39	(s,	2H,	=CH	of	coumarin),	4.56	(s,	2H,	
CH2).	MS‐EI	(m/z	(%)):	359	[M‐1]+,	187	[M‐C10H5O3]+,	145	[M‐	
C12H7O4]+.	Anal.	calcd.	for	C21H12O6:	C,	70.00;	H,	3.36.	Found:	C,	
70.12;	H,	3.48%.	
	
2.2.5.	Synthesis	of	compounds	5a‐c	
	

Mixture	 of	 compound	 4	 (0.01	 mol)	 and	 N‐heterocyclic	
quaternary	 salts	 (pyridinium,	 quinolinium	 and	 isoquino‐
linium)	 ethyl	 iodide	 (0.01	mol)	were	 dissolved	 in	 ethanol	 20	
mL	and	piperidine	0.7	mL	were	 added	 .The	 reaction	mixture	
was	 refluxed	 for	 10‐12	 h,	 filtered	 hot,	 cooled,	 neutralized	 by	
0.3	 mL	 acetic	 acid	 and	 poured	 into	 50	 mL	 ice‐water.	 The	
precipitated	solid	were	collected	and	crystallized	from	ethanol	
to	give	the	corresponding	dyes	5a‐c	(Scheme	1).	

2‐(1‐Ethylpyridin‐4(1H)‐ylidene)‐1,3‐bis(2‐oxo‐2H‐chromen	
‐3‐yl)propane‐1,3‐dione	 (5a):	 Color:	 Yellow	 powder.	 Yield:	
60%.	 M.p.:	 140‐142	 °C.	 IR	 (KBr,	 ν,	 cm‐1):	 2923	 (C‐H),	 1714	
(Lactone),	 1605	 (CO).	 Anal.	 calcd.	 for	 C28H19NO6:	 C,	 72.25;	H,	
4.11;	N,	3.01.	Found:	C,	72.35;	H,	4.18;	N,	3.11%.	UV/Vis	(EtOH,	
λmax,	nm,	()):	420	(5.33). 

2‐(1‐Ethylquinolin‐4(1H)‐ylidene)‐1,	3‐bis(2‐oxo‐2H‐chro	
men‐3‐yl)propane‐1,3‐dione	 (5b):	 Color:	 Deep	 red	 powder.	
Yield:	 60%.	 M.p.:	 165‐167	 °C.	 IR	 (KBr,	 ν,	 cm‐1):	 2921	 (C‐H),	
1714	 (lactone),	 1606	 (CO),	 2856	 (N‐ethyl).	 Anal.	 calcd.	 For	
C32H21NO6	:	C,	74.56;	H,	4.11;	N,	2.72.	Found:	C,	74.42;	H,	4.10;	
N,	2.68%.	UV/Vis	(EtOH,	λmax,	nm,	()):	470	(3.28).	

2‐(2‐Ethylisoquinoin‐1(2H)‐ylidene)‐1,3‐bis(2‐oxo‐2H‐chro	
men‐3‐yl)propane‐1,3‐dione	 (5c):	 Color:	 Pale	 yellow	 powder.	
Yield:	 55%.	 M.p.:	 145‐147	 °C.	 IR	 (KBr,	 ν,	 cm‐1):	 2925	 (C‐H),	
1715	(lactone),	1606	(CO),	1853	(N‐ethyl).	1H	NMR	(500	MHz,	
CDCl3,	δ,	ppm):	1.03	(t,	3H,	CH3	of	N‐ethyl),	3.45	(q,	2H,	CH2	of	
N‐ethyl),	5.95	(d,	1H,	isoquinoline),	6.60‐7.80	(m,	12H	(Ar‐H)	+	
1H	 (isoquinoline),	 8.55	 (s,	 2H,	=CH	of	 coumarin).	Anal.	 calcd.	
For	 C32H21NO6:	 C,	 74.56;	H,	 4.11;	N,	 2.72.	 Found:	 C,	 74.46;	H,	
4.14;	N,	2.70%.	UV/Vis	(EtOH,	λmax,	nm,	()):	410	(1.82).	
	
2.2.6.	Synthesis	of	compounds	6a‐c	
	

Mixture	of	compound	4	(0.01	mol)	and	(0.02	mol)	2(4)‐N‐
heterocyclic	 quaternary	 salts	 [α‐(γ)	 picoline,	 and	 quinaldine]	
ethyl	 iodide	 were	 dissolved	 in	 20	 mL	 ethanol	 and	 0.7	 mL	
piperidine,	 reaction	mixture	was	 refluxed	 for	 8‐10	h,	 filtered	
hot,	cooled,	neutralized	by	0.3	mL	acetic	acid	and	poured	into	
50	 mL	 ice‐water.	 The	 precipitated	 solid	 were	 collected	 and	
crystallized	from	ethanol	to	give	the	corresponding	dyes	6a‐c	
(Scheme	1). 

1‐Ethyl‐2‐((1E,	3E,	5Z)‐5‐(1‐ethylpyridin‐2(1H)‐ylidene)‐2,4‐
bis(2‐oxo‐2H‐chromen‐3‐yl)penta‐1,3‐dienyl)pyridinium	 iodide	
(6a):	 Color:	 Green	powder.	 Yield:	 70%.	M.p.:	 200‐	 202	 °C.	 IR	
(KBr,	ν,	cm‐1):	2921	(C‐H),	1725	(lactone),	2851‐	2922	(N‐ethyl	
and	N‐ethyl	 iodide).	 1H	NMR	(500	MHz,	CDCl3,	δ,	ppm):	6.20‐
8.89	(m,	21H,	(10	H	for	coumarin,	8H	for	heterocyclic	and	3H	
of	CH	olefinic)),	4.10	(q,	2H,	CH2	of	N‐ethyl	iodide),	3.50	(q,	2H,	
CH2	of	N‐ethyl),	1.29	(t,	3H,	CH3	of	N‐ethyl	iodide),	1.03	(t,	3H,	
CH3	of	N‐ethyl).	Anal.	calcd.	for	C37H31N2O4I:	C,	63.98;	H,	4.50;	
N,	4.03.	Found:	C,	63.85;	H,	4.70;	N,	4.12%.	UV/Vis	(EtOH,	λmax,	
nm,	()):	350	(3.12),	455	(6.86),	415	(9.16).	

1‐Ethyl‐2‐((1E,3E,5Z)‐5‐(1‐ethylquinolin‐2(1H)‐ylidene)‐2,4‐
bis(2‐oxo‐2H‐chromen‐3‐yl)‐penta‐1,	3‐dienyl)	quinolinium	
iodide	(6b):	Color:	Deep	red	powder.	Yield:	75%.	M.p.:	210‐212	
°C.	 Anal.	 calcd.	 for	 C45H35N2O4I:	 C,	 68.01;	 H,	 4.44;	 N,	 3.53.	
Found:	 C,	 68.10;	 H,	 4.49;	 N,	 3.55%.	 UV/Vis	 (EtOH,	 λmax,	 nm,	
()):	555	(4.01),	510	(4.43),	485	(4.07),	435	(2.84). 

1‐Ethyl‐4‐((1Z,	3E)‐5‐(1‐ethylpyridin‐4(1H)‐ylidene)‐2,	4‐bis	
(2‐oxo‐2H‐chromen‐3‐yl)penta‐1,	 3‐dienyl)pyridinium	 iodide	
(6c):	Color:	Dark	green	powder.	Yield:	65%.	M.p.:	180‐182	°C.	
Anal.	calcd.	for	C37H31N2O4I:	C,	63.98;	H,	4.50;	N,	4.03.	Found:	C,	
63.90;	 H,	 4.82;	 N,	 4.11%.	 UV/Vis	 (EtOH,	 λmax,	 nm,	 ()):	 545	
(1.92),	475	(1.34),	425	(1.09).	
	
2.2.7.	Synthesis	of	1‐(1,3‐dioxo‐1,3‐bis(2‐oxo‐2H‐chromen‐
3‐yl)propan‐2‐yl)pyridin‐1‐ium	iodide	(7)	
	

The	 compound	 7	 was	 carried	 out	 according	 to	 [31].	
Mixture	 of	 compound	 4	 (0.01	 mol),	 iodine	 (0.01	 mol)	 was	
dissolved	 in	 50	 mL	 pyridine.	 The	 reaction	 mixture	 was	
refluxed	for	1	h,	on	a	water	bath,	filtered	hot,	concentrated	and	
cooled.	 The	 precipitated	 products	 after	 dilution	 with	 50	 mL	
water	were	collected	and	crystallized	from	aqueous	ethanol	to	
give	the	corresponding	compound	7	(Scheme	1).	Color:	Brown	
powder.	Yield:	80%.	M.p.:	185‐187	°C.	 IR	(KBr,	 ν,	cm‐1):	2920	
(C‐H),	 1721	 (lactone),	 1610	 (carbonyl).	 1H	 NMR	 (500	 MHz,	
CDCl3,	 δ,	 ppm):	 7.35‐8.45	 (m,	 13H,	 Ar‐H	 (8H)	 +	 pyridinium	
iodide	 (5H)),	 8.55	 (s,	 2H,	 =CH	 of	 coumarin),	 5.45	 (s,	 1H,	
aliphatic	proton).	Anal.	calcd.	for	C26H16O6NI	:	C,	55.24;	H,	2.85;	
N,	2.48.	Found:	C,	55.28;	H,	2.78;	N,	2.52%. 
 
2.2.8.	Synthesis	of	compounds	8a‐c	
	

Mixture	of	compound	4	(0.01	mol)	with	(0.03	mol)	2(4)‐N‐
heterocyclic	 quaternary	 salts	 [α‐(γ)	 picoline,	 and	 quinaldine]	
ethyl	 iodide	 were	 dissolved	 in	 20	 mL	 ethanol	 and	 0.7	 mL	
piperidine,	reaction	mixture	was	refluxed	for	8‐10	h	 ,	 filtered	
hot,	cooled,	neutralized	by	0.3	mL	acetic	acid	and	poured	into	
50	 mL	 ice‐water.	 The	 precipitated	 solid	 were	 collected	 and	
crystallized	from	ethanol	to	give	the	corresponding	dyes	8a‐c	
(Scheme	1).	

1‐Ethyl	 ‐2‐((1E,3Z,5E)‐5‐(1‐ethylpyridin‐2(1H)‐ylidene)‐3‐
(4‐((Z)	‐(1‐ethylpyridin‐2	(1H)‐ylidene)methyl)pyridinium‐1‐yl)‐
2,	4‐bis(2‐oxo‐2H‐chromen‐3‐yl)penta‐1,	3‐dienyl)pyridinium	
iodide	 (8a):	 Color:	Green	powder.	 Yield:	 75%.	M.p.:	 205‐	207	
°C.	 Anal.	 calcd.	 for	 C50H44N4O4	 I2	 :	 C,	 58.95;	 H,	 4.35;	 N,	 5.50.	
Found:	 C,	 58.90;	 H,	 4.28;	 N,	 5.41%.	 UV/Vis	 (EtOH,	 λmax,	 nm,	
()):	425(1.74).	

1‐Ethyl‐2‐((1E,	3Z,	5E)‐5‐(1‐ethylquinolin‐2(1H)‐ylidene)‐3‐
(4‐((Z)‐(1‐ethylquinolin‐2(1H)‐ylidene)methyl)pyridinium‐1‐yl)‐
2,	4‐bis(2‐oxo‐2H‐chromen‐3‐yl)penta‐1,	3‐dienyl)quinolinium	
iodide	 (8b):	 Color:	 Deep	 red	 powder.	 Yield:	 70%.	M.p.:	 215;‐
217	 °C.	 IR	 (KBr,	 ν,	 cm‐1):	 2920	 (C‐H),	 1721	 (lactone),	 2853‐
2923	(N‐ethyl	and	N‐ethyl	iodide),	2920	(C‐H),	1721	(lactone),	
2853‐	 2923	 (N‐ethyl	 and	 N‐ethyl	 iodide).	 Anal.	 calcd.	 for	
C62H50N4O4I2:	 C,	 63.71;	 H,	 4.31;	 N,	 4.79.	 Found:	 C,	 63.79;	 H,	
4.22;	N,	 4.88%.	UV/Vis	 (EtOH,	 λmax,	 nm,	 ()):	 695	 (1.50),	 520	
(1.74),	480	(1.56),	415	(1.37).	

1‐Ethyl‐4‐((1E,3Z)‐5‐(1‐ethylpyridin‐4(1H)‐ylidene)‐3‐(4‐(1‐
ethylpyridin‐4(1H)‐ylidene)methyl)pyridinium‐1‐yl)‐2,	4‐bis(2‐
oxo‐2H‐chromen‐3‐yl)penta‐1,3‐dienyl)pyridinium	 iodide	 (8c):	
Color:	Dark	green	powder.	Yield:	60%.	M.p.:	220‐	222	°C.	Anal.	
calcd.	 for	 C50H44N4O4I2	 :	 C,	 58.94;	 H,	 4.35;	 N,	 5.50.	 Found:	 C,	
58.99;	 H,	 4.38;	 N,	 5.55%.	 UV/Vis	 (EtOH,	 λmax,	 nm,	 ()):	 450	
(2.06).	
	
2.2.9.	Synthesis	of	complexes	9a‐c	
	

The	 compounds	9a‐c	were	 carried	 out	 according	 to	 [31‐
35].	A	mixture	of	compound	4	(0.01	mol)	and	metal	dichloride	
(copper,	 cobalt	 and	 nickel)	 (0.01	 mol)	 were	 dissolved	 in	
absolute	ethanol	30	mL.	The	reaction	mixture	was	refluxed	for	



Mohamed	and	AbuEl‐Hamd	/	European	Journal	of	Chemistry	7	(1)	(2016)	66‐72	 69	
 

1‐3	h,	filtered	hot	and	concentrated.	The	precipitated	products	
were	 isolated	 and	 recrystallized	 from	 ethanol	 to	 give	 the	
corresponding	compounds	9a‐c	(Scheme	1).	

(Z)‐(3‐Oxo‐1,	 3‐bis(2‐oxo‐2H‐chromen‐3‐yl)prop‐1‐enyloxy)	
copper	 chloride	 salt	 (9a):	 Color:	 Green	 powder.	 Yield:	 70%.		
M.p.:	 220‐	 222	 °C.	 Anal.	 calcd.	 for	 C21H11O6CuCl:	 C,	 55.03;	 H,	
2.42.	Found:	C,	55.13;	H,	4.48%. 

(Z)‐(3‐Oxo‐1,	 3‐bis(2‐oxo‐2H‐chromen‐3‐yl)prop‐1‐enyloxy)	
cobalt	 chloride	 salt	 (9b):	 Color:	 Brown	 powder.	 Yield:	 45%.		
M.p.:	 235‐	 237	 °C.	 IR	 (KBr,	 ν,	 cm‐1):	 515	 (M‐O),	 2923	
(heterocyclic	 metal	 chelate),	 1704	 (CO).	 Anal.	 calcd.	 for	
C21H11O6CoCl:	C,	55.59;	H,	2.44.	Found:	C,	55.64;	H,	2.48%.	

(Z)‐(3‐Oxo‐1,	 3‐bis(2‐oxo‐2H‐chromen‐3‐yl)prop‐1‐enyloxy)	
nickel	chloride	salt	(9c):	Color:	Dark	green	powder.	Yield:	40%.	
M.p.:	 245‐247	 °C.	 Anal.	 calcd.	 for	 C21H11O6NiCl:	 C,	 55.62;	 H,	
2.45.	Found:	C,	55.60;	H,	2.40%.	
	
2.2.10.	Synthesis	of	dyes	10a‐e	
	

Mixture	of	compounds	9a‐c	(0.01	mol),	[α‐(γ)	picoline,	and	
quinaldine]ethyl	 iodide	(0.01	mol)	and	0.7	mL	piperidine	was	
added.	The	reaction	mixture	was	heated	to	30	min.	on	a	sand	
bath,	cooled,	triturated	with	30	mL	ethanol	and	refluxed	for	1	
h,	filtered	hot,	concentrated	and	cooled,	neutralized	by	0.3	mL	
acetic	acid	and	poured	into	50	mL	ice‐water.	The	precipitated	
solid	were	collected	and	crystallized	 from	ethanol	 to	give	 the	
corresponding	dyes	10a‐e	(Scheme	1).	

((Z)‐2‐((E)‐(1‐Ethylpyridin‐2(1H)ylidene)methyl)‐3‐oxo‐1,3‐
bis(2‐oxo‐2H‐chromen‐3‐yl)‐prop‐1‐enyloxy)copper	 chloride	
salt,	 mono‐5[2]‐methine	 cyanine	 dye	 (10a):	 Color:	 Green	
powder.	 Yield:	 60%.	 M.p.:	 190‐192	 °C.	 Anal.	 calcd.	 for	
C29H20NO6CuCl:	 C,	 60.32;	H,	3.49;	N,	2.43.	Found:	C,	 60.39;	H,	
3.41;	N,	2.48%.	UV/Vis	 (EtOH,	 λmax,	 nm,	 ()):	 570	 (1.15),	 410	
(1.93).	

((Z)‐2‐((E)‐(1‐Ethylquinolin‐2(1H)	ylidene)	methyl)‐3‐oxo‐
1,3‐bis(2‐oxo‐2H‐chromen‐3‐yl)‐prop‐1‐enyloxy)copper	 chloride	
salt,	 mono‐5[2]‐methine	 cyanine	 dye	 (10b):	 Color:	 Deep	 red	
powder.	 Yield:	 70%.	 M.p.:	 195‐197	 °C.	 Anal.	 calcd.	 for	
C33H22NO6CuCl:	 C,	 63.16;	H,	3.53;	N,	2.23.	Found:	C,	 63.11;	H,	
3.48;	N,	2.28%.	UV/Vis	 (EtOH,	 λmax,	 nm,	 ()):	 580	 (2.19),	 550	
(1.60),	520	(1.23),	400	(1.63).	

(Z)‐(2‐((1‐ethylpyridin‐4(1H)	ylidene)	methyl)‐3‐oxo‐1,	3‐bis	
(2‐oxo‐2H‐chromen‐3‐yl)‐prop‐1‐enyloxy)copper	 chloride	 salt,	
mono‐5[4]‐methine	 cyanine	 dye	 (10c):	 Color:	 Dark	 green	
powder.	 Yield:	 65%.	 M.p.:165‐167	 °C.	 Anal.	 calcd.	 for	
C29H20NO6CuCl:	 C,	 60.32;	H,	3.49;	N,	2.43.	Found:	C,	 60.38;	H,	
3.52;	N,	2.51%.	UV/Vis	 (EtOH,	 λmax,	 nm,	 ()):	 500	 (2.29),	 470	
(2.17),	440	(2.36),	420	(2.22).	

((Z)‐2‐((E)‐(1‐ethylquinolin‐2(1H)	ylidene)	methyl)‐3‐oxo‐1,	
3‐bis(2‐oxo‐2H‐chromen‐3‐yl)prop‐1‐enyloxy)cobalt	 chloride	
salt,	 mono‐5[2]‐methine	 cyanine	 dye	 (10d):	 Color:	 Deep	
reddish	violet	powder.	Yield:	75%.	M.p.:	220‐222	°C.	IR	(KBr,	ν,	
cm‐1):	 525‐535	 (O‐M‐O),	 2923	 (N‐ethyl),	 1720	 (CO).	 Anal.	
calcd.	 for	C33H22NO6CoCl:	C,	 63.63;	H,	3.56;	N,	2.25.	Found:	C,	
63.69;	 H,	 3.60;	 N,	 2.31%.	 UV/Vis	 (EtOH,	 λmax,	 nm,	 ()):	 690	
(5.55),	580	(1.83),	560	(1.61),	480	(1.58).	

((Z)‐2‐((E)‐(1‐ethylquinolin‐2(1H)	ylidene)	methyl)‐3‐oxo‐1,	
3‐bis(2‐oxo‐2H‐chromen‐3‐yl)prop‐1‐enyloxy)nickel	 chloride	
salt,	mono‐5[2]‐methine	cyanine	dye	(10e):	Color:	Deep	reddish	
violet	 powder.	 Yield:	 70%.	 M.p.:	 180‐182	 °C.	 Anal.	 calcd.	 for	
C33H22NO6NiCl:	 C,	 63.65;	H,	 3.56;	N,	 2.25.	 Found:	 C,	 63.75;	H,	
3.62;	N,	2.31%.	UV/Vis	 (EtOH,	 λmax,	 nm,	 ()):	 670	 (4.36),	 580	
(1.62),	510	(1.11).	
	
2.3.	Antimicrobial	activity	
	

Different	concentrations	(50,	100,	150	and	200	µg/mL)	of	
CdCl2	 and	 CoCl2	 were	 added	 to	 flasks	 that	 contain	 nutrient	
media	 and	 20	 ml	 saline	 solution	 (20%).	 All	 flasks	 were	
sterilized	 in	 Autoclave.	 After	 sterilization	 the	 media	 were	
poured	 in	 Petri	 dishes.	 Small	 halls	 were	 made	 in	 the	 solid	

media	 by	 using	 corckoporer.	 Each	 microorganism	 species	
(clinical	isolated)	was	inoculated	separately	in	saline	solution.	
20	mL	from	each	solution	that	contain	organisms	was	added	to	
the	hall	 in	solid	media	plates.	All	plates	were	 incubated	at	37	
°C	 for	 days.	 All	 procedure	 was	 repeated	 with	 the	 synthetic	
organic	 compounds	 and	 antibiotic	 (Tetracycline	 and	 ampi‐
cillin)	as	positive	control.	Growth	was	measured	(mm)	under	
the	 treatment	 with	 different	 concentrations	 of	 heavy	 metals	
compared	to	control.		
	
3.	Results	and	discussion	
	
3.1.	Chemistry	
	

Reaction	of	a	ratio	of	1	mol	of	3‐acetylchromen‐2‐one	(1)	
[30]	in	presence	of	iodine	with	the	heterocyclic	nitrogen	base	
(pyridine)	in	excess	amount	afforded	the	corresponding	1‐(2‐
oxo‐2H‐chromene‐3‐carbonyl)pyridinium	 iodide	 (2)	 [30].	
Thermal	 basic	 hydrolysis	 of	 the	 key	 intermediate	 2	 using	
aqueous	 ethanolic	 solution	 of	 sodium	 hydroxide	 gave	 the	
corresponding	sodium	salt	of	coumarin‐3‐sodium	carboxylate	
which	on	triturating	with	concentrated	HCl,	the	free	2‐oxo‐2H‐
chromene‐3‐carboxylic	 acid	 (3)	 is	 formed.	 Reaction	 of	
equimolar	ratio	of	compound	3‐acetylchromen‐2‐one	(1)	with	
2‐oxo‐2H‐chromene‐3‐carboxylic	 acid	 (3),	 under	 thermal	
piperidine	 catalysis	 conditions	 gave	 the	 corresponding	
starting	compound	4	namely	as	1,3‐bis‐(2‐oxo‐2H‐chromen‐3‐
yl)	 propane‐1,3‐dione.	 Reaction	 of	 equimolar	 ratios	 of	
compound	 4	 with	 N‐ethyl	 heterocyclic	 quaternary	 salt	
(pyridine,	 quinoline	 and	 isoquinoline)	 iodide	 in	 the	presence	
of	 piperidine	 as	 basic	 catalyst	 afforded	 symmetrical	 2‐(1‐
ethylpyridin‐4(1H)‐ylidene)‐1,	 3‐bis(2‐oxo‐2H‐chromen‐3‐yl)	
propane‐1,3‐dionemero	 cyanine	 monomethine	 like	 2[4]	 dye	
5a,	 and	 the	 other	 derivatives	5b,	 and	5c.	 Treatment	 of	 such	
resulted	 compounds	5a‐c	with	 concentrated	H2SO4,	 solubility	
take	place	with	no	liberating	iodine	vapor	on	warming.	This	a	
criteria	 that	 the	 reaction	 is	 suggested	 to	 proceed	 through	
oxidative	 elimination	 reaction	 between	 active	 hydrogen	 of	
heterocyclic	 quaternary	 salt	 and	 active	 methylene	 group	 of	
started	 compound	 4	 followed	 by	 dehydrohalogenation	 ‐HI	
processes	 afforded	 the	 desired	 dyes	 5a‐c.	 Also,	 reaction	 of	
equimolar	ratios	of	compound	4	with	bi	molar	ratios	of	2(4)‐
methyl	 heterocyclic	 quaternary	 salt	 [α‐(γ)	 picoline,	 and	
quinaldine]ethyl	 iodide	 under	 basic	 catalyst	 conditions	
afforded	the	corresponding	symmetrical	1‐ethyl‐2‐((1E,3E,5Z)‐
5‐(1‐ethylpyidin‐2(1H)ylidene)‐2,4‐bis‐(2‐oxo‐2H‐chromen‐3‐
yl)penta‐1,3‐dienyl)pyrdinium	 iodide	 pentamethine	 cyanine	
dye	6a,	and	other	derivatives	6b	and	6c.	

Reaction	of	a	ratio	of	1	mol	of	compound	4	in	presence	of	
iodine	with	the	heterocyclic	nitrogen	base	(pyridine)	in	excess	
amount	 afforded	 the	 corresponding	 N‐substituted	 hetero	
cyclidinium	ylide	iodide	7	[31].	Further	reaction	of	equimolar	
ratios	 of	 compound	 7	 with	 3	 molar	 ratios	 of	 2(4)‐N‐methyl	
heterocyclic	 quaternary	 salt	 [α‐(γ)	 picoline,	 and	 quinaldine]	
ethyl	 iodide	 under	 basic	 catalyst	 conditions	 afforded	 the	
corresponding	 1‐ethyl‐2‐((1E,3Z,5E)‐5‐(1‐ethylpyridin‐2(1H)	
ylidene)‐3‐(4‐((Z)‐(1‐ethylpyridin‐2(1H‐lidene)methyl)pyridi‐	
nium‐1‐yl)‐2,4‐bis(2‐oxo‐2H‐chromen‐3‐yl)penta‐1,3‐dienyl)	
pyridinium	 iodide	 pentamethine	 cyanine	 dye	 8a,	 and	 other	
derivatives	8b	and	8c.		

On	 the	 other	 hand,	 reaction	 of	 equimolar	 ratios	 of	
compound	4	with	metal	dichloride	(copper,	cobalt	and	nickel)	
in	absolute	ethanol	gave	the	corresponding	complexes,	namely	
as	 (Z)‐(3‐oxo‐1,3‐bis(2‐oxo‐2H‐chromen‐3‐yl)prop‐1‐enyloxy)	
copper(cobalt	and/or	nickel)	chloride	salt	complexes	9a‐c	[32‐
38]	which	 consider	 as	 a	 key	 intermediate	 compounds	 in	 the	
synthesis	 of	 metal	 complex	 cyanine	 dyes.	 Thus,	 reaction	 of	
equimolar	 ratio	 of	 compounds	 9a‐c	 with	 2(4)‐N‐methyl	
heterocyclic	 quaternary	 salt	 [α‐(γ)	 picoline,	 and	 quinaldine]	
ethyl	 iodide	 under	 thermal	 condition	 in	 the	 presence	 of	
piperidine	as	basic	catalyst	afforded	the	corresponding		



70	
	

	
Table	1.	The	el
Compound	
5a	
5b	
5c	
6a	
6b 
6c	
8a 
8b	
8c	
10a	
10b	
10c	
10d	
10e	
*	s	=	shoulder.	
	
	
((Z)‐2‐((E)‐(
bis(2‐oxo‐2H
salt,	 mono‐
derivatives	
compounds	
soluble	in	it	
indicates	 th
reaction.	 Th
proceed	thro
hydrogen	of	
active	 hydro
chelate	 ring	
above	cyanin
	
3.2.	UV‐Vis	a
	

The	 expe
newly	synthe
shown	in	Fig
in	Table	1.	T
in	 the	 visi
coefficients	
especially	 fo
10a‐e.	

	

	
Figure	1.	Absor

	
The	 visib

cyanine	 dye
chromic	 sh
quaternary	r
moieties	 M.	
compound	 5
resulted	 in	
increasing	
delocalizatio
linkage	posit
to	 4‐	 in	 com

ectronic	absorptio

1‐ethylpyridin‐
H‐chromen‐3‐yl
‐5[2]‐methine	
10b,	 10c,	 10
10a‐e	on	tritur
with	no	liberat
hat	 these	 dyes
his	 a	 criteria	 t
ough	oxidative	e
methyl	group	
ogen	 of	 site	 5
followed	by	de
ne	dyes	10a‐e	[

absorption	spe

erimental	 UV‐V
esized	cyanine	
gures	1‐3	and	t
The	results	sho
ible	 waveleng
(εmax)	 and	 acco
or	 monomethin

rption	spectra	for	

ble	 absorption	
es	 in	 ethanol	
ift	 depending	
residue	A,	their	
	 Thus,	 substit
5a	 by	 A	 =	 N
a	 bathochromi
of	 ‐conjuga

on	 in	 quinoline	
tion	of	quinolin
mpound	 5b	 re

Mohame

on	spectra	of	new	s
UV‐Vis	spectra
420,	
470 
410 
530,	455,	415 
555,	510,	485,	4
545,	475,	425 
425 
695,	520,	480,	4
450 
570,	410	
580,	550s,	520s
500,	470,	440,	4
690,	580,	560s,	
670,	580,	510	

‐2(1H)ylidene)m
l)‐prop‐1‐enylo
cyanine	 dye

0d	 and	 10e	
rating	with	conc
ting	iodine	vap
s	 10a‐e	 libera
that	 the	 reacti
elimination	rea
of	heterocyclic
5	 of	 2‐metalo‐
ehydrohalogen
[31].	

ctra	

Vis	 spectra	 in	 9
dyes	5a‐c,	6a‐c
their	spectral	d
w	 intense,	broa
gth	 region	 wi
ompanied	with	
ne	 cyanine	 dye

cyanine	dyes	5a‐c	

maxima	 of	 the
undergo	 batho
on	 the	 natu
linkage	positio
tution	 of	 A	 =
N‐ethylquinoline
ic	 shift	 of	 Δλm
ation	 and	 m
moiety.	Analog
ne	residue	from
esulted	 in	 a	 ba

ed	and	AbuEl‐Ha

synthesized	cyanin
,	λ	max		(nm) *	

435 

415 

,	400	
420s	
480s	

methyl)‐3‐oxo‐
oxy)copper,	 ch
e	 10a,	 and	
(Scheme	 1).
centrated	H2SO
por	on	warming
ated	 HI	 durin
ion	 is	 suggest
action	between	
c	quaternary	sa
1,3‐dioxinium	
ation	 ‐HI	 to	giv

95%	 ethanol	 fo
c,	8a‐c	and	10a
data	are	summa
ad	absorption	
ith	 high	 extin
strong	 fluores

es	 of	 metal	 com

in	95%	ethanol	so

e	 newly	 synthe
ochromic	 or	 h
ure	 of	 hetero
on	and	metal	div
	 N‐ethylpyridi
e	 in	 compoun
max	 =	 50	 nm	 fo
more	 extensiv
gously,	 changin
m	1‐	in	compou
athochromic	 sh

md /	European	J

ne	dyes	5a‐c,	6a‐c,	

1,3‐
loride	
other	
These	
O4	acid	
g.	This	
g	 the	
ted	 to	
active	
alt	and	
metal	
ve	 the	

or	 the	
a‐e	are	
arized	
bands	
nction	
scence	
mplex	

	

olution.	

esized	
hypso‐
ocyclic	
valent	
ine	 in	
nd	 5b	
or	 the	
ve	 	
ng	 the	
und	5c	
hift	 of				

Δλm
‐co
pos
abs
infl
sub
=	 N
bath
abs
attr
Cha
pyr
bath
Add
mes
infl
sub
=	 N
bath
new
attr
ium
from
resu
nm
pyr

	
Figu

dye
qua
Thu
10a
in	a
ban
at	5

Journal	of	Chemis

8a‐c	and	10a‐e	in

max	=	60	nm.	Th
onjugation	with
sition	 1‐	 of	
orption	 spectr
uenced	 by	 he
bstitution	of	A	=
N‐ethylquinolin
hochromic	shif
orption	 bands	
ributed	 to	 the	
anging	 the	 lin
ridin‐2	ium	in	d
hochromic	 shi
ditionally,	 the	 v
so‐substituted‐
uenced	 by	 he
bstitution	of	A	=
N‐ethylquinolin
hochromic	 shif
w	absorption	ba
ributed	 to	 the	m
m	moiety.	Chang
m	 pyridin‐2‐iu
ulted	in	bathoc
.	 This	 is	 due	
ridine‐4‐ium	mo
	

ure	2.	Absorption	s
	
The	 visible	 ab
es	 of	 metal	 co
aternary	hetero
us,	 substitution
a	by	A	=	N‐ethy
a	bathochromic
nds	with	the	app
520	and	550	nm

stry	7	(1)	(2016)

n	95%	ethanol.	
εmax		(mol‐1	c
5333
3277
1817	
3120,	6860,	
4012,	4427,	
1920,	1335,	
1738
15000,	1738
2062
1151,	1926
2191,	1602,	
2285,	2169,	
555,	1832,	1
436,	1623,	1

is	could	be	attr
hin	position	4‐	
isoquinoline	
ra	 of	 pentamet
terocyclic	 qua
=	N‐ethylpyridin
n‐2‐ium	 in	 co
ft	of	Δλmax	=	15	
at	 485	 and	 5
more	 extensiv

nkage	 position
dye	6a	to	pyridi
ift	 of	 the	 wav
visible	 absorpt
pentamethine	
terocyclic	 qua
=	N‐ethylpyridin
n‐2‐ium	 in	 co
ft	 of	 Δλmax	 =	 55
ands	at	520	and
more	extensive
ging	the	linkage
um	 in	 dye	 8a
chromic	shift	of
to	 the	 more

oiety.	

spectra	for	cyanine

bsorption	 spec
omplex	 10a‐e
ocyclic	residue	A
n	 of	 A	 =	N‐ethy
ylquinolin‐2‐ium
c	shift	of	Δλmax	=
pearance	new	s
m,	respectively.		

)	66‐72	

cm‐1)	

9160 
4065,	2837 
1085	

8,	1556,	1373 

1215,	1634	
2361,	2222	
614,	1575	
105	

ributed	to	the	m
of	quinoline	ri
moieties.	 Also
thine	 cyanine	
aternary	 salts	
n‐2‐ium	in	com
ompound	 6b	
nm	with	the	ap
510	 nm,	 respec
ve	 ‐conjugati
n	 of	 pyridine	
in‐4	ium	in	dye
velength	 of	 Δλ
ion	 spectra	 of	
cyanine	 dy

ternary	 salts	
n‐2‐ium	in	com
ompound	 8b	
5	 nm	with	 the	
d	695	nm,	respe
e	‐conjugation
e	position	of	py
to	 pyridin‐4‐i
f	the	wavelengt
	 extensive	 ‐c

e	dyes	8a‐c	in	95%

tra	 of	 monom
e	 depend	 on	
A	and	metal	div
ylpyridin‐2‐ium
m	in	compound
=	10	nm	of	red
shoulders	of	ab

more	extensive
ing	rather	than
o,	 the	 visible
dyes	 6a‐c	 are
residue.	 Thus,

mpound	6a	by	A
resulted	 in	 a
ppearance	new
ctively.	 This	 is
on	 in	 dye	 6b.
residue	 from

e	6c	resulted	in
λmax	 =	 10	 nm.
monomethine‐
es	 8a‐c	 are
residue	 A.	 So,

mpound	8a	by	A
resulted	 in	 a
appearance	 of
ectively.	This	is
n	 in	quinolin‐2‐
yridine	residue
um	 in	 dye	 8c
th	of	Δλmax	=	25
conjugation	 in

	

%	ethanol	solution.

ethine	 cyanine
the	 nature	 of
valent	moieties.
m	 in	 compound
d	10b	 resulted
d	and	blue	shift
sorption	bands

e	
n	
e	
e	
,	
A	
a	
w	
s	
.	

m	
n	
.	
‐
e	
,	
A	
a	
f	
s	
‐
e	
c	
5	
n	

e	
f	
.	
d	
d	
t	
s	



	
Table	2.	The	ef
Strains	

Streptococcus	s
Staphylococcus	
Salmonella	spp	
Shigella	spp	
	

	
This	 is	 a

dye	 10b.	 Ch
from	 pyridin
resulted	in	b
nm	 of	 the	 b
absorption	 b
other	 hand,	
than	those	 in
of	both	size	
of	 positive	
hypsochrom
cation	 comp
dioxine	ring	
	

	
Figure	 3.	 Abs
solution.	
	
	
3.3.	Antimic
	

Newly	 s
chosen	 to	 s
chemical	stru
compounds	
Staphylococc
corckoporer	
synthetic	 ch
than	the	ant
bacterial	 str
bacterial	 str
synthetic	 co
represented	
growth	 of	 th
inhibition	ef
This	may	be	
5a	 comparin
isoquinoline	
material	at	p
	
4.	Conclusio
	

In	this	w
with	 potent
structures	 w

Mo

ffect	of	some	select
Growth	(
Positive	
control	

spp.	 5	
s	spp	 5	

5	
5	

attributed	 to	 th
hanging	 the	 lin
n‐2‐ium	 in	 dye
bathochromic	sh
blue	 shift	 abso
bands	 at	 470	
dyes	 having	 C
ncluded	Ni2+	an
and	effective	ch
charge	 of	 me

mic	 shift	 which
plex	 of	 ion	 pai
similar	to	the	e

sorption	 spectra	 f

crobial	activity

synthesized	 cy
tudy	 the	 biolo
ucture.	The	in‐v
were	 teste

cus	 sp,	 Salmon
method.	 Antim

hemical	 compou
ibiotics	in	inhib
rains.	 The	 gro
rains	 by	 differ
ompounds	 wer
in	 Table	 2.	 Th
he	 tested	 strain
ffect	while	 the	
due	to	the	pres
ng	 with	 the	 d
	and	quinaldin
positions	1	and	

ons	

work,	new	cyani
tial	 biologically
were	 confirmed

ohamed	and	Abu

ted	synthesized	co
(mm)	

4	(mg/L)	
50	 100	
5	 5	
5	 5	
5	 5	
5	 5	

he	more	 extens
nkage	 position	
e	 10a	 to	 pyridi
hift	of	the	wave
orption	 band	 w
and	 440	 nm,	 r
o2+	 show	more
nd/or	Cu2+.	Thi
harge	of	metal	
etal	 cation	 (N
h	 corresponds	
ir	 of	 oxygen	 a
effects	of	proton

for	 cyanine	 dyes	

y	of	some	select

anine	 dyes	 5a
ogical	 activity	
vitro	susceptibi
ed	 against	
ella	 sp.	 and	 S
microbial	 sens
unds	 proved	 t
biting	the	grow
owth	 inhibitio
rent	 concentra
re	 recorded	 a
he	 dye	5a	 has	
ns,	 dyes	 5c	 an
starting	compo
sence	of	N‐ethyl
dyes	 5c	 and	 6
e	rings	connect
2,	respectively	

ine	dyes	5a‐c,	6
y	 active	 were
d	 by	 IR,	 1H	 N

uEl‐Hamd /	Euro

mpounds	4,	5a,	5c

6
150	 200 5
5	 5	 5
5	 5	 5
5	 5 6
5	 5 6

sive	‐conjugat
of	 pyridine	 re
in‐4‐ium	 in	 dy
elength	of	Δλma
with	 the	 appea
respectively.	 O
e	 bathochromic
s	 is	due	to	incr
cation	and	incr
Ni	 and	 Cu)	 ca
to	 a	 more	 in

atom	 in	 the	 m
nation.	

10a‐e in	 95%	 e

ted	cyanine	dye

a,	 5c	 and	 6b
and	 its	 relatio
lities	of	the	syn
Streptococcus

Shigella	 sp.	 by	
sibility	 of	 the	 t
to	 be	 more	 eff
wth	of	the	patho
ons	 of	 the	 se
ations	 of	 the	 t
and	 the	 data	
strong	 effect	 o
nd	 6b	 showed	
ound	4	has	no	
l	pyridine	ring	
6b	 which	 conta
ted	with	the	st
[39].	 

6a‐c,	8a‐c	and	
	 synthesized.	
NMR	 and	 elem

opean	Journal	of	
 

c	and	6b	at	differen

6b	(mg/L)	
0 100 150
.2	 5.8	 7.3	
.6	 6.4	 7.8	
.2 7.1 8.6
.5 7.5 8.9

ion	 in	
esidue	
ye	 10c	
ax	=	10	
arance	
On	 the	
c	 shift	
reases	
reases	
ausing	
ntense	
metalo‐

	

ethanol	

es	

were	
on	 the	
nthetic	
s	 sp,	
using	
tested	
fective	
ogenic	
lected	
tested	
were	

on	 the	
slight	
effect.	
in	dye	
aining	
tarting	

10a‐e	
Their	

mental	

ana
com
sho
hete
met
5a
anti
dre
pro
con
row
	
Ack
	

(Re
like
of	B
	
Ref
	
[1].

[2].

[3].

[4].

[5].

[6].
[7].

[8].

[9].

[10]

[11]

[12]

[13]
[14]

[15]

[16]

[17]
[18]

[19]

[20]

[21]

[22]

[23]

[24]

Chemistry	7 (1)	(

nt	concentration	o

5a	(mg
200 50 1
8.6	 6.7	 9
9.1	 7.2	 1
9.3 7.7 1
9.5 8.3 1

alysis	 techniqu
mpounds	 in	 et
owed	 that	 the	 a
erocyclic	 quate
tal	divalent	mo
is	 potent	 com
ibiotic	for	the	t
am	to	future	is
oved	safe,	 there
nserve	 the	 hard
w	materials	of	th

knowledgemen

This	study	wa
esearch	 Project
e	 to	 thank	the	 l
Biology,	Aswan	

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