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European	Journal	of	Chemistry	7	(2)	(2016)	146‐151	

	

European	Journal	of	Chemistry	
ISSN	2153‐2249	(Print)	/	ISSN	2153‐2257	(Online)		2016	Atlanta	Publishing	House	LLC	‐	All	rights	reserved	‐	Printed	in	the	USA	

http://dx.doi.org/10.5155/eurjchem.7.2.146‐151.1393	

	
	

	

	

European	Journal	of	Chemistry	
Journal	webpage:	www.eurjchem.com	 	

	 	 	

Synthesis	and	studies	on	chromene	based	reactive	azo	dyes		
and	their	applications	on	different	fabrics	

Mohamed	Gomaa	Badrey	1,*,	Sobhi	Mohamed	Gomha	2	and	Hamada	Moustafa	Mashaly	3	

1	Chemistry	Department,	Faculty	of	Science,	Fayoum	University,	El‐Fayoum,	63514,	Egypt	
2	Department	of	Chemistry,	Faculty	of	Science,	University	of	Cairo,	Giza,	12613,	Egypt	
3	Dyeing	and	Printing	Department,	Textile	Division,	National	Research	Center,	Giza,	12622,	Egypt	

*	Corresponding	author	at:	Chemistry	Department,	Faculty	of	Science,	Fayoum	University,	El‐Fayoum,	63514,	Egypt.		
Tel.:	+2.084.6338462.	Fax:	+2.084.6370025.	E‐mail	address:	mgb00@fayoum.edu.eg	(M.G.	Badrey).	

	
	

	 	

	 	 	

ARTICLE	INFORMATION	 	 ABSTRACT	

	
DOI:	10.5155/eurjchem.7.2.146‐151.1393	

Received:	07	January	2016	
Accepted:	07	February	2016	
Published	online:	30	June	2016	
Printed:	30	June	2016	

	 A	 number	 of	 reactive	 azo	 dyes	 based	 on	 chromene	 moiety	 were	 prepared	 through	 two
inversed	 routes	 using	 2‐amino‐7‐hydroxy‐4‐phenyl‐4H‐chromene‐3‐carbonitrile,	 which
when	coupled	to	different	diazonium	salts,	yielded	the	corresponding	dyes	which	were	then
further	reacted	with	cyanuric	chloride.	The	structures	of	the	prepared	dyes	were	elucidated
from	their	spectral	data,	elemental	analyses	and	colour	measurements.	Dyeing	of	cellulosic
and	 nylon	 fibers	 using	 the	 prepared	 dyes	 was	 done	 under	 suitable	 conditions.	 Some
properties	 of	 the	 prepared	 dyes	 such	 as	 fastness	 properties	 (washing,	 rubbing	 and
perspiration)	 and	 colour	 measurements	 were	 investigated.	 The	 dyes	 showed	 very	 good
fastness	 to	 washing	 properties	 when	 attached	 to	 nylon	 fibers	 but	 poor	 fastness	 to	 light
properties	were	shown.	

KEYWORDS	
Chromene	
Diazonium	salts	
Fastness	to	light	
Reactive	azo	dyes	
Cyanauric	chloride	
Fastness	to	washing	

Cite	this:	Eur.	J.	Chem.	2016,	7(2),	146‐151	

	
1.	Introduction	
	

A	versatile	number	of	heterocyclic	compounds	are	widely	
used	 in	 dye	 chemistry	 especially	 azo	 dyes	 ones.	 Azo	 dyes	
containing	 heterocyclic	 moieties	 show	 brighter	 and	 often	
deeper	shades	than	their	benzene	analogs.	On	the	other	hand,	
such	type	of	dyes	are	quite	 important	as	disperse	dyes	which	
used	 for	 dyeing	 polyester	 fibers;	 also,	 they	 are	 important	 as	
functional	 dye,	 nonlinear	 optical	 systems,	 photodynamic	
therapy	 and	 lasers	 [1‐7].	 From	 the	 heterocycles	 used	 for	
synthesis	 of	 azo	 dyes	 are	 chromene	 derivatives	 commonly	
used	 for	 production	 of	 highly	 effective	 fluorescent	 dyes	 for	
synthetic	 fibers	 and	 daylight	 fluorescent	 pigments	 [8‐13].	
Among	 azo	 dyes,	 reactive	 ones	 have	 an	 important	 place	 and	
could	be	used	for	dyeing	various	fabrics.	

Reactive	 dyes	 are	 colored	 compounds	which	 contain	 one	
or	 two	 groups	 capable	 of	 forming	 covalent	 bonds	 to	 fibers.	
These	 bonds	 formed	 between	 a	 carbon	 atom	 or	 phosphorus	
atom	 of	 the	 dyes	 ion	 or	 molecules	 and	 an	 oxygen	 atom,	
nitrogen	 atom	 or	 sulfur	 atom	 of	 a	 hydroxyl,	 an	 amino	 or	 a	
mercapto	group,	respectively,	of	the	substrate	[14].	These	dyes	
are	generally	used	on	higher	value	clothes,	which	are	normally	
mercerized	[15].	

Reactive	dyes	 though	 late	entry	 into	 the	field	of	synthetic	
dyes,	 very	 soon	 attained	 a	 commercial	 status.	 Several	 new	
reactive	 systems	 have	 been	 introduced	 from	 time	 to	 time,	
which	 covers	 the	 subject	 of	 innumerable	 patents	 and	
publication	[16].	It	was	for	the	first	time	that	dyeing	has	been	
done	 by	 chemical	 reaction	 between	 the	 dye	 and	 the	 fiber,	
enabling	one	 to	get	assortment	of	bright,	 attractive	shades	of	
adequate	fastness	with	considerable	ease	of	dyeing.		

Moreover,	 reactive	dyes	 exhibit	 a	wide	 range	of	 different	
chemical	 structures,	 primarily	 based	 on	 substituted	 aromatic	
and	 heterocyclic	 groups.	 Reactive	 dyes	 are	 one	 of	 the	 most	
commonly	used	dyes	for	textile	printing	because	of	their	high	
wet	 fastness,	 brilliant	 colors	 and	 variety	 of	 hue	 [17].	 In	
general,	 reactive	dyes	used	in	printing	often	have	a	degree	of	
fixation	of	only	60%,	whereas	in	dyeing,	a	degree	of	fixation	of	
over	 90%	 can	 be	 achieved	 [18].	 A	 large	 number	 of	 reactive	
dyes	are	azo	compounds	that	are	linked	by	an	azo	bridge	[19].	
Reactive	dyes	are	extensively	used	in	many	industries	such	as	
textiles,	rubber,	paper,	leather	cosmetics	and	pharmaceuticals.	
In	addition,	they	are	characterized	by	ease	of	applications	and	
minimum	energy	consumption.		

	
	



Badrey	et	al.	/	European	Journal	of	Chemistry	7	(2)	(2016)	146‐151	 147	
 

	

	
	

Scheme	1
	
	
For	 these	 reasons,	 herein,	 we	 reported	 a	 synthesis	 of	

number	 of	 new	 reactive	 azo	 dyes	 starting	 from	 2‐amino‐7‐
hydroxy‐4‐phenyl‐4H‐chromene‐3‐carbonitrile	 (1)	 through	
different	alternative	pathways.	
	
2.	Experimental	
	
2.1.	Instrumentation	

	
Melting	points	were	measured	on	Electrothermal	IA	9000	

series	 digital	 melting	 point	 apparatus.	 The	 IR	 spectra	 were	
recorded	in	potassium	bromide	discs	on	a	Pye	Unicam	SP	3300	
and	Shimadzu	FT‐IR	8101	PC	 infrared	spectrophotometer.	 1H	
NMR	 and	 13C	 NMR	 spectra	 were	 recorded	 in	 deuterated	
dimethyl	sulfoxide	(DMSO‐d6)	using	a	Varian	Gemini	300	NMR	
spectrometer	 (300	 MHz	 for	 1H	 NMR).	 Mass	 spectra	 were	
recorded	on	a	Shimadzu	GCMS‐QP1000	EX	mass	spectrometer	
at	 70	 eV.	 Elemental	 analysis	 was	 carried	 out	 at	 the	
Microanalytical	 Centre	 of	 Cairo	 University,	 Giza,	 Egypt.	 All	
reactions	were	followed	by	TLC	(Silica	gel,	Merck).	
	
2.2.	Synthesis	

	
2‐Amino‐4‐phenyl‐7‐hydroxychromene‐3‐carbonitrile	 [20,	

21]	was	prepared	as	reported	in	the	literature.	
	
2.2.1.	Synthesis	of	2‐amino‐8‐arylazo‐4‐phenyl‐7‐hydroxy	
chromene‐3‐carbonitrile	(2a‐h)	
	

To	an	ice	cold	solution	of	the	appropriate	aromatic	amine	
(0.01	mol)	in	a	mixture	of	concentrated	hydrochloric	acid	(12	
mL),	 and	water	 (15	mL),	 a	 cold	 aqueous	 solution	 of	 sodium	

nitrite	 (0.7	 g),	 was	 added	 portion	wise	 at	 0	 °C.	 The	 solution	
was	 stirred	 vigorously	 for	 1	 h	 to	 yield	 the	 diazonium	 salt	
solution	at	0‐2	°C.	The	diazonium	salt	solution	was	then	added	
drop	 wise	 to	 pre‐cooled	 (0	 °C)	 solution	 of	 compound	 1	 (2‐
amino‐7‐hydroxy‐4‐phenyl‐4H‐chromene‐3‐carbonitrile)	
(0.01	mol,	 2.64	g	 in	10	mL	ethanol	 and	5	mL	of	 10%	NaOH)	
over	 a	 period	 of	 1	 h	 with	 vigorous	 stirring	 at	 0‐3	 °C.	 The	
reaction	mixture	 was	 further	 stirred	 for	 1	 h	 at	 0‐5	 °C.	 After	
completion	 of	 the	 reaction,	 the	 products	 were	 filtered	 off,	
washed	with	water	 until	 free	 from	 acid,	 dried	 at	 40	 °C	 in	 an	
oven	to	give	compounds	2a‐h,	which	were	recrystallized	from	
appropriate	 solvent	 (Scheme	1).	 The	 synthesized	 compounds	
2a‐h	 together	with	 their	physical	and	spectral	data	are	 listed	
below.	

2‐Amino‐7‐hydroxy‐4‐phenyl‐8‐(phenyldiazenyl)	 ‐4H‐chro‐
mene‐3‐carbonitrile	(2a):	Color:	Orange.	Yield:	72%.	M.p.:	172‐
174	 °C.	 FT‐IR	 (KBr,	 ,	 cm‐1):	 1604	 (C=N),	 2189	 (CN),	 3237,	
3347	(NH2),	3440	(OH).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	
4.92	 (s,	 1H,	 Chromene	 H‐4),	 6.24	 (s,	 2H,	 D2O	 exchangeable,	
NH2),	 6.89	 (d,	 1H,	 J	 =	 9.1	 Hz,	 H‐6	 Ar),	 7.13‐7.65	 (m,	 10H,	
ArH),7.74	 (d,	 1H,	 J	 =	 9.1	 Hz,	 H‐5	 Ar),	 11.09	 (s,	 1H,	 D2O	
exchangeable,	OH).	MS	(EI,	m/z	(%)):	368	(M+,	35),	318	(32),	
197	 (35),	 118	 (32),	 93	 (100).	 Anal.	 calcd.	 for	 C22H16N4O2:	 C,	
71.73;	H,	4.38;	N,	15.21.	Found	C,	71.56;	H,	4.28;	N,	15.04%.	

2‐Amino‐8‐((4‐chlorophenyl)diazenyl)	 ‐7‐hydroxy‐4‐phenyl‐
4H‐chromene‐3‐carbonitrile	 (2b):	 Color:	 Orange.	 Yield:	 74%.	
M.p.:	188‐190	°C.	FT‐IR	(KBr,	,	cm‐1):	1621	(C=N),	2212(CN),	
3198,	3325	(NH2),	3392	(OH).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	
ppm):	 4.84	 (s,	 1H,	 Chromene	 H‐4),	 6.37	 (s,	 2H,	 D2O	
exchangeable,	NH2),	6.84	(d,	1H,	J	=	9.1	Hz,	H‐6	Ar),	7.10‐7.68	
(m,	9H,	ArH),7.89	(d,	1H,	J	=	9.1	Hz,	H‐5	Ar),	12.06	(s,	1H,	D2O	
exchangeable,	OH).	MS	 (EI,	m/z	 (%)):	 404	 (M+,	 10),	 402	 (M+,	



148	 Badrey	et	al.	/	European	Journal	of	Chemistry	7	(2)	(2016)	146‐151	
	
27),	 265	 (48),	 197	 (100),	 111	 (53),	 69	 (70).	 Anal.	 calcd.	 for	
C22H15ClN4O2:	 C,	 65.60;	 H,	 3.75;	 N,	 13.91.	 Found	 C,	 65.50;	 H,	
3.67;	N,	13.64%.	

2‐Amino‐7‐hydroxy‐4‐phenyl‐8‐(p‐tolyldiazenyl)	 ‐4H‐chro‐
mene‐3‐carbonitrile	(2c):Color:	Orange.	Yield:	75%.	M.p.:	167‐
169	 °C.	 FT‐IR	 (KBr,	 ,	 cm‐1):	 1606	 (C=N),	 2188(CN),	 3212,	
3340	(NH2),	3423	(OH).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	
2.37	(s,	3H,	CH3),	4.87	(s,	1H,	Chromene	H‐4),	6.48	(s,	2H,	D2O	
exchangeable,	NH2),	6.84	(d,	1H,	J	=	9.1	Hz,	H‐6	Ar),	7.11‐7.67	
(m,	9H,	ArH),7.70	(d,	1H,	J	=	9.1	Hz,	H‐5	Ar),	12.01	(s,	1H,	D2O	
exchangeable,	OH).	MS	(EI,	m/z	(%)):	382	(M+,	76),	337	(100),	
299	(89),	248	(75),	128	(86),	116	(73),	60	(89).	Anal.	calcd.	for	
C23H18N4O2:	C,	72.24;	H,	4.74;	N,	14.65.	Found	C,	72.12;	H,	4.56;	
N,	14.47%.	

2‐Amino‐7‐hydroxy‐8‐((4‐methoxyphenyl)diazenyl)	 ‐4‐phen	
yl‐4H‐chromene‐3‐carbonitrile	(2d):	Color:	Orange.	Yield:	73%.	
M.p.:	147‐149	°C.	FT‐IR	(KBr,	,	cm‐1):	1623	(C=N),	2189(CN),	
3216,	3335	(NH2),	3425	(OH).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	
ppm):	 3.77	 (s,	 3H,	 CH3),	 4.88	 (s,	 1H,	 Chromene	H‐4),	 6.52	 (s,	
2H,	D2O	 exchangeable,	NH2),	 6.82	 (d,	 1H,	 J	 =	 9.1	Hz,	H‐6	Ar),	
7.16‐7.68	(m,	9H,	ArH),7.73	(d,	1H,	J	=	9.1	Hz,	H‐5	Ar),	11.94	(s,	
1H,	 D2O	 exchangeable,	 OH).	 MS	 (EI,	m/z	 (%)):	 398	 (M+,	 34),	
336	(52),	243	(50),	187	(83),	147	(47),	77	(100).	Anal.	 calcd.	
for	C23H18N4O3:	C,	69.34;	H,	4.55;	N,	14.06.	Found	C,	69.18;	H,	
4.50;	N,	13.91%.	

4‐((2‐Amino‐3‐cyano‐7‐hydroxy‐4‐phenyl‐4H‐chromen‐8‐yl)	
diazenyl)benzenesulfonic	acid	 (2e):	Color:	Orange.	Yield:	70%.	
M.p.:	212‐214	°C.	FT‐IR	(KBr,	,	cm‐1):	1621	(C=N),	2190(CN),	
3247,	3329	(NH2),	3426	(OH).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	
ppm):	 4.89	 (s,	 1H,	 Chromene	 H‐4),	 6.27	 (s,	 2H,	 D2O	 exchan‐
geable,	NH2),	6.88	(d,	1H,	J	=	9.1	Hz,	H‐6	Ar),	7.17‐7.68	(m,	9H,	
ArH),7.77	 (d,	 1H,	 J	 =	 9.1	Hz,	H‐5	 Ar),	9.34,	 12.06	 (s,	 2H,	D2O	
exchangeable,	OH	and	SO3H).	MS	(EI,	m/z	(%)):	448	(M+,	66),	
391	 (70),	 272	 (64),	 191	 (70),	 151	 (71),	 134	 (79),	 64	 (100).	
Anal.	calcd.	for	C22H16N4O5S:	C,	58.92;	H,	3.60;	N,	12.49.	Found	
C,	58.78;	H,	3.46;	N,	12.32%.	

2‐Amino‐8‐((1,	 5‐dimethyl‐3‐oxo‐2‐phenyl‐2,3‐dihydro‐1H‐
pyrazol‐4‐yl)diazenyl)	 ‐7‐hydroxy‐4‐phenyl‐4H‐chromene‐3‐car	
bonitrile	(2f):	Color:	Orange.	Yield:	72%.	M.p.:	181‐183	°C.	FT‐
IR	 (KBr,	 ,	 cm‐1):	 1621	 (C=N),	 1678	 (C=O),	 2189(CN),	 3189,	
3364	(NH2),	3432	(OH).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	
2.32	(s,	3H,	CH3),	3.23	(s,	3H,	CH3),	4.88	(s,	1H,	Chromene	H‐4),	
6.48	(s,	2H,	D2O	exchangeable,	NH2),	6.86	(d,	1H,	J	=	9.1	Hz,	H‐6	
Ar),	7.17‐7.72	(m,	10H,	ArH),	7.82	 (d,	1H,	 J	=	9.1	Hz,	H‐5	Ar),	
12.01	 (s,	 1H,	 D2O	 exchangeable,	 OH).	 MS	 (EI,	m/z	 (%)):	 478	
(M+,	58),	459	(79),	380	(56),	231	(78),	199	(72),	111	(70),	55	
(100).	Anal.	 calcd.	 for	C27H22N6O3:	 C,	 67.77;	H,	 4.63;	N,	17.56.	
Found	C,	67.90;	H,	4.68;	N,	17.38%.	

2‐Amino‐7‐hydroxy‐4‐phenyl‐8‐(thiazol‐2‐yldiazenyl)	 ‐4H‐
chromene‐3‐carbonitrile	 (2g):	Color:	Orange.	Yield:	74%.	M.p.:	
193‐195	°C.	FT‐IR	(KBr,	,	cm‐1):	1621	(C=N),	2211(CN),	3217,	
3336	(NH2),	3422	(OH).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	
4.83	 (s,	 1H,	 Chromene	 H‐4),	 6.47	 (s,	 2H,	 D2O	 exchangeable,	
NH2),	6.87	(d,	1H,	 J	=	9.1	Hz,	H‐6	Ar),	7.25‐7.88	(m,	7H,	ArH),	
7.97	(d,	1H,	J	=	9.1	Hz,	H‐5	Ar),	11.33	(s,	1H,	D2O	exchangeable,	
OH).	MS	(EI,	m/z	(%)):	375	(M+,	16),	321	(38),	244	(39),	177	
(61),	95	(24),	69	(100).	Anal.	calcd.	 for	C19H13N5O2S:	C,	60.79;	
H,	3.49;	N,	18.66.	Found	C,	60.49;	H,	3.51;	N,	18.42%.	

2‐Amino‐8‐(benzo[d]thiazol‐2‐yldiazenyl)‐7‐hydroxy‐4‐phen	
yl‐4H‐chromene‐3‐carbonitrile	(2h):	Color:	Orange.	Yield:	76%.	
M.p.:	152‐154	°C.	FT‐IR	(KBr,	,	cm‐1):	1624	(C=N),	2190(CN),	
3220,	3343	(NH2),	3427	(OH).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	
ppm):	 4.84	 (s,	 1H,	 Chromene	 H‐4),	 6.42	 (s,	 2H,	 D2O	 exchan‐
geable,	NH2),	6.82	(d,	1H,	J	=	9.1	Hz,	H‐6	Ar),	7.21‐7.87	(m,	9H,	
ArH),	 7.92	 (d,	 1H,	 J	 =	 9.1	 Hz,	 H‐5	 Ar),	 11.26	 (s,	 1H,	 D2O	
exchangeable,	OH).	MS	(EI,	m/z	(%)):	425	(M+,	58),	386	(59),	
313	(58),	272	(47),	191	(56),	125	(68),	55	(87).	Anal.	calcd.	for	
C23H15N5O2S:	 C,	 64.93;	 H,	 3.55;	 N,	 16.46.	 Found	 C,	 64.76;	 H,	
3.46;	N,	16.43%.	
	

2.2.2.	Synthesis	of	2‐((4,6‐dichloro‐1,3,5‐triazin‐2‐yl)amino)	
‐7‐hydroxy‐4‐phenyl‐4H‐chromene‐3‐carbonitrile	(3)	
	

A	 solution	 of	 cyanuric	 chloride	 (3.66	 g,	 0.02	 mol)	 in	
acetone	(30	mL)	was	poured	into	a	vigorously	stirred	mixture	
of	 crushed	 ice	 (50	 g)	 and	 water	 (50	 mL).	 A	 solution	 of	
compound	1	(5.28	g,	0.02	mol)	was	added	drop	wise	at	0‐5	°C,	
over	 60	 min,	 with	 the	 pH	 maintained	 between	 3.5	 and	 4.5	
using	sodium	carbonate	solution	(10%,	w:v).	The	solution	was	
stirred	 for	 a	 further	 60	 min	 to	 complete	 the	 reaction.	 The	
product	formed	during	the	reaction	was	removed	by	filtration,	
washed	with	water	several	 times,	dried	and	crystallized	from	
ethanol	to	give	compound	3	(Scheme	1).	Color:	Creamy	white.	
Yield:	81%.	M.p.:	163‐165	°C.	FT‐IR	(KBr,	,	cm‐1):	1605	(C=N),	
2189(CN),	3335	 (NH),	3422	 (OH).	 1H	NMR	 (400	MHz,	DMSO‐
d6,	 δ,	 ppm):	 4.73	 (s,	 1H,	 Chromene	 H‐4),	 6.31(s,	 1H,	 D2O	
exchangeable,	NH),	6.67(s,	1H,	Ar‐H(8)),	6.89	(d,	1H,	J	=	9.1	Hz,	
H‐6	Ar),	7.31‐7.65	(m,	5H,	Ar‐H),7.76	(d,	1H,	J	=	9.1	Hz,	H‐5	Ar),	
11.09	 (s,	 1H,	 D2O	 exchangeable,	 OH).	 MS	 (EI,	m/z	 (%)):	 411	
(M+,	 16),	 357	 (38),	 280	 (39),	 213	 (61),	 131(24),	 105	 (100).	
Anal.	 calcd.	 for	 C19H11Cl2N5O2:	 C,	 55.36;	 H,	 2.69;	 N,	 16.99.	
Found	C,	55.32;	H,	2.56;	N,	16.68%.	
	
2.2.3.	Synthesis	of	2‐(4,6‐dichloro‐[1,3,5]triazin‐2‐ylamino)‐
8‐arylazo‐7‐hydroxy‐4‐phenylchromene‐3‐carbonitrile	(4a‐
h)	
	

Method	A:	A	solution	of	 cyanuric	 chloride	 (0.915	g,	0.005	
mol)	in	acetone	(20	mL)	was	poured	into	a	vigorously	stirred	
mixture	of	crushed	ice	(50	g)	and	water	(30	mL).	A	solution	of	
compound	2a‐h	 (0.005	 mol)	 was	 added	 dropwise	 at	 0‐5	 °C,	
over	 60	 min,	 with	 the	 pH	 maintained	 between	 3.5	 and	 4.5	
using	sodium	carbonate	solution	(10%,	w:v).	The	solution	was	
stirred	 for	 a	 further	 60	 min	 to	 complete	 the	 reaction.	 The	
product	formed	during	the	reaction	was	removed	by	filtration,	
washed	with	water	several	 times,	dried	and	crystallized	from	
appropriate	solvent	to	give	compounds	4a‐h	(Scheme	1).	

Method	 B:	 To	 an	 ice	 cold	 solution	 of	 the	 appropriate	
aromatic	 amine	 (0.001	 mol)	 in	 a	 mixture	 of	 concentrated	
hydrochloric	 acid	 (7	mL)	 and	water	 (15	mL),	 a	 cold	 aqueous	
solution	of	sodium	nitrite	(0.1	g),	was	added	portion	wise	at	0	
°C.	 The	 solution	was	 stirred	 vigorously	 for	 1	 hr	 to	 yield	 the	
diazonium	salt	solution	at	0‐2	°C.	The	diazonium	salt	solution	
was	 then	 added	 drop	 wise	 to	 pre‐cooled	 (0	 °C)	 solution	 of	
compound	3	(0.001	mol,	0.411	g	in	10	mL	ethanol	and	3	mL	of	
10%	NaOH)	over	a	period	of	1	hr	with	vigorous	stirring	at	0‐3	
°C.	The	reaction	mixture	was	further	stirred	for	1	hr	at	0‐5	°C.	
After	completion	of	the	reaction,	the	products	were	filtered	off,	
washed	with	water	 until	 free	 from	 acid,	 dried	 at	 40	 °C	 in	 an	
oven	 to	 give	 compound	 4a‐h	 (Scheme	 1).	 The	 synthesized	
compounds	 4a‐h	 together	 with	 their	 physical	 and	 spectral	
data	are	listed	below.	

2‐((4,6‐Dichloro‐1,3,5‐triazin‐2‐yl)amino)‐7‐hydroxy‐4‐phen	
yl‐8‐(phenyldiazenyl)‐4H‐chromene‐3‐carbonitrile	 (4a):	 Color:	
Orange.	 Yield:	 68%.	 M.p.:	 220‐222	 °C.	 FT‐IR	 (KBr,	 ,	 cm‐1):	
1602	(C=N),	2190	(CN),	32145	(NH),	3432	(OH).	1H	NMR	(400	
MHz,	DMSO‐d6,	 δ,	ppm):	4.92	 (s,	1H,	Chromene	H‐4),	6.83	 (d,	
1H,	J	=	9.2	Hz,	H‐6	Ar),	7.09‐7.60	(m,	10H,	ArH),	7.78	(d,	1H,	J	=	
9.2	Hz,	H‐5	Ar),	9.54	(s,	1H,	D2O	exchangeable,	NH),	11.21	(s,	
1H,	D2O	exchangeable,	OH).	MS	(EI,	m/z	(%)):	518	(M++2,	50),	
517	 (M++1,	 49),	 516	 (M+,	 95),	 421	 (84),	 302	 (82),	 232	 (69),	
165	 (75),	93	 (100),	77	 (67).	Anal.	 calcd.	 for	C25H15Cl2N7O2:	C,	
58.15;	H,	2.93;	N,	18.99.	Found	C,	58.12;	H,	2.76;	N,	18.67%.	

8‐((4‐Chlorophenyl)diazenyl)‐2‐((4,6‐dichloro‐1,3,5‐triazin‐
2‐yl)	 amino)	 ‐7‐hydroxy‐4‐phenyl‐4H‐chromene	 ‐3‐carbonitrile	
(4b):	Color:	Orange.	Yield:	68%.	M.p.:	172‐173	°C.	FT‐IR	(KBr,	
,	 cm‐1):	 1601	 (C=N),	 2192	 (CN),	 3237	 (NH),	 3419	 (OH).	 1H	
NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	4.87	(s,	1H,	Chromene	H‐4),	
6.71	(d,	1H,	J	=	9.2	Hz,	H‐6	Ar),	7.10‐7.64	(m,	9H,	ArH),	7.78	(d,	
1H,	 J	 =	9.2	Hz,	H‐5	Ar),	10.04	 (s,	 1H,	D2O	exchangeable,	NH),	
11.32	 (s,	 1H,	 D2O	 exchangeable,	 OH).	 MS	 (EI,	m/z	 (%)):	 552	



Badrey	et	al.	/	European	Journal	of	Chemistry	7	(2)	(2016)	146‐151	 149	
 

(M++2,	12),	551	(M++1,	27),	550	(M+,	33),	404	 (58),	303	(48),	
254	 (40),	 197	 (69),	 80	 (92),	 64	 (100).	 Anal.	 calcd.	 for	
C25H14Cl3N7O2:	 C,	 54.52;	H,	 2.56;	N,	 17.80.	 Found	C,	 54.44;	H,	
2.38;	N,	17.62%.	

2‐((4,6‐Dichloro‐1,3,5‐triazin‐2‐yl)amino)‐7‐hydroxy‐4‐phen	
yl‐8‐(p‐tolyldiazenyl)‐4H‐chromene‐3‐carbonitrile	 (4c):	 Color:	
Orange.	 Yield:	 67%.	 M.p.:	 193‐195	 °C.	 FT‐IR	 (KBr,	 ,	 cm‐1):	
1584	(C=N),	2191	(CN),	3241	(NH),	3440	(OH).	1H	NMR	(400	
MHz,	 DMSO‐d6,	 δ,	 ppm):	 2.32	 (s,	 3H,	 CH3),	 4.97	 (s,	 1H,	
Chromene	H‐4),	6.86	(d,	1H,	J	=	9.1	Hz,	H‐6	Ar),	7.11‐7.68	(m,	
9H,	 ArH),	 7.73	 (d,	 1H,	 J	=	 9.1	 Hz,	 H‐5	 Ar),	10.01	 (s,	 1H,	 D2O	
exchangeable,	 NH),	 11.12	 (s,	 1H,	 D2O	 exchangeable,	 OH).	 MS	
(EI,	m/z	(%)):	530	(M+,	46),	432	(46),	334	(38),	262	(50),	174	
(33),	80	(94),	64	(100).	Anal.	calcd.	for	C26H17Cl2N7O2:	C,	58.88;	
H,	3.23;	N,	18.49.	Found	C,	58.59;	H,	3.20;	N,	18.32%.		

2‐((4,6‐Dichloro‐1,3,5‐triazin‐2‐yl)amino)‐7‐hydroxy‐8‐	 ((4‐
methoxyphenyl)diazenyl)‐4‐phenyl‐4H‐chromene‐3‐carbonitrile	
(4d):	Color:	Yellow.	Yield:	72%.	M.p.:	158‐160	°C.	FT‐IR	(KBr,	
,	 cm‐1):	 1601	 (C=N),	 2190	 (CN),	 3278	 (NH),	 3442	 (OH).	 1H	
NMR	 (400	MHz,	DMSO‐d6,	 δ,	ppm):	3.87	 (s,	 3H,	CH3),	 4.83	 (s,	
1H,	Chromene	H‐4),	6.88	(d,	1H,	J	=	9.1	Hz,	H‐6	Ar),	7.11‐7.85	
(m,	9H,	ArH),	7.97	(d,	1H,	J	=	9.1	Hz,	H‐5	Ar),	10.23	(s,	1H,	D2O	
exchangeable,	 NH),	 11.13	 (s,	 1H,	 D2O	 exchangeable,	 OH).	 MS	
(EI,	m/z	 (%)):	 546	 (M+,	 8),	 488	 (10),	 336	 (8),	 282	 (11),	 158	
(12),	80	(100),	64	(70).	Anal.	calcd.	for	C26H17Cl2N7O3:	C,	57.16;	
H,	3.14;	N,	17.95.	Found	C,	57.03;	H,	3.12;	N,	17.76%.	

4‐((3‐Cyano‐2‐((4,	6‐dichloro‐1,	3,	5‐triazin‐2‐yl)amino)	 ‐7‐
hydroxy‐4‐phenyl‐4H‐chromen‐8‐yl)	 diazenyl)	 benzenesulfonic	
acid	(4e):	Color:	Red.	Yield:	66%.	M.p.:	166‐168	°C.	FT‐IR	(KBr,	
,	 cm‐1):	 1600	 (C=N),	 2192	 (CN),	 3241	 (NH),	 3424	 (OH).	 1H	
NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	4.90	(s,	1H,	Chromene	H‐4),	
6.86	(d,	1H,	J	=	9.1	Hz,	H‐6	Ar),	7.18‐7.74	(m,	9H,	ArH),	7.84	(d,	
1H,	 J	=	9.1	Hz,	H‐5	Ar),	10.12	 (s,	 1H,	D2O	exchangeable,	NH),	
11.14,	13.14	(s,	2H,	D2O	exchangeable,	OH	and	SO3H).	MS	(EI,	
m/z	(%)):	595	(M+,	54),	467	(68),	384	(45),	238	(59),	153	(60),	
80	(100),	64	(66).	Anal.	calcd.	for	C25H15Cl2N7O5S:	C,	50.35;	H,	
2.54;	N,	16.44.	Found	C,	50.22;	H,	2.34;	N,	16.23%.	

2‐((4,6‐Dichloro‐1,3,5‐triazin‐2‐yl)amino)‐8‐((1,	5‐dimethyl‐
3‐oxo‐2‐phenyl‐2,	 3‐dihydro‐1H‐pyrazol‐4‐yl)	 diazenyl)‐7‐hyd	
roxy‐4‐phenyl‐4H‐chromene‐3‐carbonitrile	 (4f):	 Color:	 Yellow.	
Yield:	69%.	M.p.:	201‐203	°C.	FT‐IR	(KBr,	,	cm‐1):	1611	(C=N),	
1678	 (C=O),	2189(CN),	 3360	 (NH),	3430	 (OH).	 1H	NMR	 (400	
MHz,	 DMSO‐d6,	 δ,	 ppm):	 2.34	 (s,	 3H,	 CH3),	 3.28	 (s,	 3H,	 CH3),	
5.10	 (s,	 1H,	 Chromene	H‐4),	 6.84	 (d,	 1H,	 J	 =	 9.3	Hz,	H‐6	 Ar),	
7.11‐7.79	(m,	10H,	ArH),	7.88	(d,	1H,	J	=	9.3	Hz,	H‐5	Ar),	10.04	
(s,	1H,	D2O	exchangeable,	NH),	11.87	(s,	1H,	D2O	exchangeable,	
OH).	MS	(EI,	m/z	(%)):	626	(M+,	14),	496	(27),	357	(16),	231	
(18),	 199	 (22),	 80	 (100),	 64	 (66).	 Anal.	 calcd.	 for	
C30H21Cl2N9O3:	 C,	 57.52;	H,	 3.38;	N,	 20.12.	 Found	C,	 57.36;	H,	
3.24;	N,	20.02%.	

2‐((4,	6‐Dichloro‐1,	3,	5‐triazin‐2‐yl)amino)‐7‐hydroxy‐4‐
phenyl‐8‐(thiazol‐2‐yldiazenyl)	 ‐4H‐chromene‐3‐carbonitrile	
(4g):	Color:	Brown.	Yield:	66%.	M.p.:	184‐186	°C.	FT‐IR	(KBr,	
,	 cm‐1):	 1613	 (C=N),	 2210(CN),	 3326	 (NH),	 3409	 (OH).	 1H	
NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	5.23	(s,	1H,	Chromene	H‐4),	
6.87	(d,	1H,	J	=	9.1	Hz,	H‐6	Ar),	7.15‐7.82	(m,	7H,	ArH),	7.92	(d,	
1H,	 J	 =	9.1	Hz,	H‐5	Ar),	10.27	 (s,	 1H,	D2O	exchangeable,	NH),	
11.26	 (s,	 1H,	 D2O	 exchangeable,	 OH).	 MS	 (EI,	m/z	 (%)):	 523	
(M+,	17),	388	(68),	269	(79),	151	(68),	80	(93),	64	(100).	Anal.	
calcd.	for	C22H12Cl2N8O2S:	C,	50.49;	H,	2.31;	N,	21.41.	Found	C,	
50.37;	H,	2.38;	N,	21.29%.	

8‐(Benzo[d]thiazol‐2‐yldiazenyl)‐2‐((4,	 6‐dichloro‐1,	 3,	 5‐
triazin‐2‐yl)amino)	 ‐7‐hydroxy‐4‐phenyl‐4H‐chromene‐3‐carbo	
nitrile	(4h):	Color:	Yellow.	Yield:	68%.	M.p.:	210‐212	°C.	FT‐IR	
(KBr,	,	cm‐1):	1614	(C=N),	2217(CN),	3358	(NH),	3426	(OH).	
1H	NMR	(400	MHz,	DMSO‐d6,	 δ,	ppm):	4.73	 (s,	1H,	Chromene	
H‐4),	6.84	(d,	1H,	 J	=	9.1	Hz,	H‐6	Ar),	7.12‐7.79	(m,	9H,	ArH),	
7.93	(d,	1H,	J	=	9.1	Hz,	H‐5	Ar),	10.16	(s,	1H,	D2O	exchangeable,		
	

NH),	 11.21	 (s,	 1H,	D2O	 exchangeable,	 OH).	MS	 (EI,	m/z	 (%)):	
573	 (M+,	 45),	 501	 (100),	 459	 (76),	 358	 (70),	 260	 (70),	 190	
(88),	82	(93),	60	(10).	Anal.	calcd.	for	C26H14Cl2N8O2S:	C,	54.46;	
H,	2.46;	N,	19.54.	Found	C,	54.40;	H,	2.23;	N,	19.33%.	
	
2.3.	Dyeing	
	
2.3.1.	Materials		
	

All	 chemicals	 were	 laboratory	 reagent	 grade.	 Bleached	
100%	cotton	fabric	(140	g/m2)	was	supplied	by	El‐Mahalla	El‐
Kobra	Company.	The	fabrics	were	scoured	in	aqueous	solution	
with	 a	 liquor	 ratio1:50	 containing	 5	 g/L	 nonionic	 detergent	
solution	(Hostapal,	Clariant)	and	2	g/L	Na2CO3	at	95	°C	for	4	h	
to	 remove	 impurities,	 then	 rinsed	 thoroughly	 in	 cold	 tap	
water,	and	dried	at	 room	temperature.	Bleached	100%	nylon	
fabric	 (129	 g/m2)	 was	 supplied	 by	 El‐Mahalla	 El‐Kobra	
Company.	The	fabrics	were	scoured	in	aqueous	solution	with	a	
liquor	ratio1:50	containing	5	g/L	nonionic	detergent	solution	
(Hostapal,	Clariant)	at	50	°C	for	30	min	to	remove	impurities,	
then	 rinsed	 thoroughly	 in	 cold	 tap	water,	 and	 dried	 at	 room	
temperature.	
	
2.3.2.	Dyeing	of	cotton	with	dichlorotriazine	reactive	dyes	
	

Dyeing	process	was	carried	out	at	40	 °C,	Liquor	 to	goods	
ratio	(L.R.)	1:30	deing	bath	contains	2%	weight	of	fiber	(w.o.f)	
dye,	sodium	chloride	35	g/L,	the	fabric	were	immersed	and	the	
temperature	were	raised	to	40	°C.	The	alkali	sodium	carbonate	
30	g/L	was	added	after	30	min	and	 the	dyeing	continued	 for	
another	30	min.	At	the	end	of	dyeing,	 the	dyed	samples	were	
rinsed	with	tap	water	and	allowed	to	dry	in	open	air.	
	
2.3.3.	Dyeing	of	nylon	with	hydrolyzed	reactive	dye	
	

Dyeing	process	was	 carried	out	 at	95	 °C.	Dyeing	bath	pH	
adjusted	to	5	using	acetic	acid	solution.	The	dyeing	continued	
for	60	min.	At	the	end	of	dyeing,	the	dyed	samples	were	rinsed	
with	tap	water	and	allowed	to	dry	in	open	air.	
	
3.	Results	and	discussion		

	
3.1.	Chemistry	
	

In	general,	 azo	dyes	have	been	prepared	 through	various	
pathways	either	by	diazotization	or	other	alternative	methods	
[22,23].	 In	 the	 present	 work,	 a	 series	 of	 chromene	 based	
reactive	 azo	 dyes	were	prepared	 using	 the	 compound	1	 as	 a	
coupling	 component	 with	 different	 diazotized	 aromatic	 and	
heteroaromatic	 amines.	 The	 phenolic	 ring	 of	 compound	 1	 is	
quite	 much	 reactive	 towards	 electrophilic	 reagents	 such	 as	
diazonium	salts	and	two	possible	positions	can	couple	with	the	
attacking	 electrophilic	 diazonium	 salt.	 These	 positions	 are	 6	
and	 8,	 however,	 indeed	 one	 position	 only	 coupled	 to	 the	
reagent	 (position	 8)	 [24].	 Aromatic	 and	 heteroaromatic	
amines	were	 converted	 into	 diazonium	 salts	 then	 coupled	 to	
the	chromene	compound	1	in	faintly	basic	medium	(NaOH)	to	
produce	the	azo	dyes	2a‐h.	The	resulting	dyes	themselves	are	
not	 the	main	 target	 of	 this	 project	 but	 they	 could	 be	used	 in	
further	 treatment	 for	production	of	newly	 reactive	dyes.	 The	
use	 of	 2,4,6‐trichlorotriazine	 (cyanauric	 chloride)	 can	 fulfill	
the	 required	 purpose	 which	 can	 act	 as	 an	 intervening	 unit	
between	the	dye	molecule	and	polymeric	fibrous	material	such	
as	cotton	and	wool.	

For	 the	 preparation	 of	 the	 required	 reactive	 dyes,	 two	
synthetic	routes	could	be	followed	which	could	be	considered	
as	 reverse	 of	 each	 other.	 First,	 aromatic	 and	 heteroaromatic	
amines	 were	 diazotized	 and	 then	 added	 portion	 wise	 to	 an	
alkaline	solution	of	the	chromene	1	to	afford	the	dyes	2a‐h.		

	
	



150	 Badrey	et	al.	/	European	Journal	of	Chemistry	7	(2)	(2016)	146‐151	
	

	 	
Table	1.	Fastness	properties	of	the	dyed	cotton	fabrics	with	the	reactive	dyes	a.	
Sample	 Washing	 Perspiration	 Rubbing	 Light	

Alkaline Acidic
St.**	 St.*	 Alt.	 St.**	 St.* Alt. St.** St.* Alt. Wet	 Dry	

1	 4	 4	 3‐4	 3‐4	 4	 3‐4	 4	 4	 3‐4	 3	 4	 4	
2	 4	 4	 4	 4	 4	 3‐4	 4	 4	 4	 3‐4	 4	 4	
3	 3‐4	 2‐3	 3‐4	 3‐4	 4 3 3‐4 4 3 4	 4	 2
4	 4	 3‐4	 4	 3‐4	 4	 3‐4	 3‐4	 4	 3‐4	 4	 4	 2	
5	 4	 4	 3	 3‐4	 4	 3‐4	 3‐4	 4	 3‐4	 3‐4	 4	 2	
6	 4	 4	 3	 3‐4	 4 3 4 4 4 4	 4	 4
7	 4	 4	 3	 3‐4	 4 3 4 4 4 4	 4	 3‐4
a	Alt.:	Alteration;	St:	Staining,	*	Staining	on	cotton;	**	Staining	on	wool.	
	
	

These	dyes	in	turn	reacted	with	2,4,6‐trichlorotriazine	in	a	
mixture	 of	 acetone	 and	water	 at	 low	 temperature	 at	 pH	 =	 7	
and	 the	 products	 formed	 during	 the	 reaction	 separated	 by	
filtration	to	give	the	reactive	azodyes	4a‐h.		

The	 second	 route	 achieved	by	 treating	 compound	1	with	
cyanauric	chloride	under	same	conditions	as	in	the	first	route	
giving	compound	3	which	was	coupled	smoothly	with	various	
diazonium	salts	furnishing	compounds	4a‐h.	The	second	route	
thought	 to	 be	 better	 than	 the	 first	 one	 as	 it	 includes	 less	
reaction	steps	and	thus	saving	chemicals.	
	
3.2.	Fastness	properties	[25‐30]	
	 	
3.2.1.	Color	fastness	to	washing 
	

The	 color	 fastness	 to	washing	was	 determined	 according	
to	 the	 method	 ISO	 105‐C02	 (1989)	 [31].	 The	 composite	
specimens	were	sewed	between	two	pieces	of	bleached	cotton	
and	wool	fabrics,	and	then	immersed	into	an	aqueous	solution	
containing	5	g/L	non‐ionic	detergents	at	liquor	ratio	1:50.	The	
bath	 was	 thermostatically	 adjusted	 to	 60	 °C	 and	 50	 °C	 for	
cotton	 and	 nylon	 fabric,	 respectively,	 for	 30	 min.	 After	 the	
desired	 time,	 samples	 were	 removed,	 rinsed	 twice	 with	
occasional	 hand	 squeezing,	 and	 then	 dried.	 Evaluation	 of	 the	
wash	 fastness	was	 established	 using	 the	 Grey‐scale	 for	 color	
change	1,	poor;	2,	fair;	3,	moderate;	4,	good;	5,	excellent.	
	
3.2.2.	Color	fastness	to	rubbing	
	

Color	fastness	to	rubbing	was	determined	according	to	the	
test	method	ISO	105‐X12	(1987)	[32].	The	test	is	designed	for	
determining	the	degree	of	color,	which	may	transfer	from	the	
surface	of	the	colored	fibers	to	other	surface,	by	rubbing.	The	
current	test	can	be	carried	out	on	dry	and	wet	fibers.		
	
3.2.2.1.	Dry	crocking	test	
	

The	test	specimen	was	placed	flat	on	the	base	of	the	crock‐
meter.	A	white	testing	cloth	was	mounted.	The	covered	finger	
was	lowered	on	to	the	test	specimen	and	caused	to	slide	back	
and	forth	20	 times	by	making	ten	complete	 turns	at	a	 rate	of	
one	 turn/sec.	 The	 white	 test	 sample	 was	 then	 removed	 for	
evaluation	using	the	Grey‐scale	for	staining:	1,	poor;	2,	fair;	3,	
moderate;	4,	good;	5,	excellent.	
	
3.2.2.2.	Wet	crocking	test	
	

The	white	test	sample	was	thoroughly	wetted	out	in	water	
to	 a	 65%	 and	 then	 picked	 up.	 The	 procedure	 was	 run	 as	
before.	 The	 white	 test	 samples	 were	 air	 dried	 before	
evaluation:	1,	poor;	2,	fair;	3,	moderate;	4,	good;	5,	excellent.	
	
3.2.3.	Color	fastness	to	perspiration	
	

Two	 artificial	 perspiration	 solutions	 were	 prepared	 as	
follows	 according	 to	 test	 method	 ISO	 105‐E04	 (1989)	 [33];	
acidic	and	alkaline	solutions.	

Acidic	 solution	was	 prepared	 by	 dissolving	 of	L‐histidine	
monohydrochloride	monohydrate	 (0.5	 g),	 sodium	chloride	 (5	
g)	and	sodium	dihydrogen	orthophosphate	dihydrate	(2.2	g)	in	
one	 liter	 distilled	water.	 Then	 the	pH	was	 finally	 adjusted	 to	
5.5	 using	 0.1	 N	 NaOH.	 To	 prepare	 the	 alkaline	 solution,	 L‐
histidine	 monohydrochloride	 monohydrate	 (0.5	 g),	 sodium	
chloride	 (5	 g)	 and	 disodium	 hydrogen	 orthophosphate	
dihydrate	(2.5	g)	were	all	dissolved	in	one	liter	distilled	water.	
The	pH	was	adjusted	to	8	using	0.1	N	NaOH.		

The	 fastness	 test	 was	 performed	 as	 follows.	 The	 colored	
specimen	5×4	cm	was	sewed	between	two	pieces	of	uncolored	
specimens	 to	 form	 composite	 specimen.	 The	 composite	
samples	were	immersed	for	15‐30	min.	in	both	solutions	with	
a	proper	agitation	and	squeezing	 to	 insure	complete	wetting.	
The	test	specimens	were	placed	between	two	plates	of	glass	or	
plastic	under	a	force	of	about	4‐5	kg.	The	plates	containing	the	
composite	 specimens	 were	 then	 held	 vertical	 in	 an	 oven	 at	
37±2	°C	for	4	hours.		

The	 effect	 on	 the	 color	 of	 the	 tested	 specimens	 was	
expressed	 and	 defined	 by	 reference	 to	 Grey‐scale	 for	 color	
change:	1,	poor;	2,	fair;	3,	moderate;	4,	good;	5,	excellent.	
	
3.2.4.	Color	fastness	to	light	
	

The	light	fastness	test	was	carried	out	in	accordance	with	
test	method	 ISO	105‐B02	(1988)	 [34]	using	carbon	arc	 lamp,	
continuous	 light,	 for	 35	 hours.	 The	 effect	 on	 the	 color	 of	 the	
tested	 samples	 was	 recorded	 by	 reference	 to	 Blue‐scale	 for	
color	change	1,	poor;	3,	moderate;	5,	good;	8,	very	good	[25].		
	
3.2.5.	Fastness	properties	
	
3.2.5.1.	Fastness	to	washing		
	

As	 shown	 in	 Table	 1,	 the	 dyed	 cotton	 fabrics	 have	 very	
good	fastness	to	washing	according	to	international	Geometric	
Grey	 scale	 with	 exception	 of	 dye	 3	 which	 gives	 fear	 result.	
Also,	in	Table	2,	the	dyed	nylon	fabrics	have	very	good	fastness	
to	 washing	 according	 to	 international	 Geometric	 Grey	 scale	
with	exception	of	dye	3	which	gives	 fear	 result	as	a	 result	of	
surface	coloration.	
	
3.2.5.2.	Fastness	to	perspiration	(Acid	and	alkaline)	
	

The	high	rating	for	change	 in	 the	color	at	both	acidic	and	
alkaline	 conditions	 indicates	 that	 the	 sensitivity	 of	 the	 dyed	
samples	is	not	related	to	pH.	This	may	be	due	to	the	stability	of	
the	 dyes	 towards	 degradation	 under	 either	 acidic	 or	 basic	
conditions.	

	
3.2.5.3.	Fastness	to	Rubbing	
	

The	 test	 is	 designed	 to	 determine	 the	 amount	 of	 color	
transferred	 from	 the	 surface	 of	 colored	 fabrics	 to	 another	
surface	by	rubbing.	Most	of	the	dyes	have	a	moderate	rubbing	
fatness	and	this	may	be	attributed	to	adequate	diffusion	of	dye	
molecule	into	the	fabrics.	
	



Badrey	et	al.	/	European	Journal	of	Chemistry	7	(2)	(2016)	146‐151	 151	
 

	
Table	2.	Fastness	properties	of	the	dyed	nylon	fabrics	a.	
Sample	 Washing	 Perspiration	 Rubbing	 Light	

Alkaline Acidic
St.**	 St.*	 Alt.	 St.**	 St.*	 Alt.	 St.**	 St.*	 Alt.	 Wet	 Dry	

1	 4	 3	 4	 3‐4	 4 4 4 4 4 3	 3	 3
2	 4	 4	 4	 3‐4	 4 4 4 4 4 3‐4	 4	 3‐4
3	 3‐4	 2‐3	 3	 3‐4	 4 3‐4 4 4 4 2‐3	 2‐3	 2‐3
4	 4	 3‐4	 4	 3‐4	 4	 3‐4	 4	 4	 3‐4	 2‐3	 3‐4	 2‐3	
5	 4	 4	 3‐4	 3‐4	 4	 3‐4	 4	 4	 4	 2‐3	 3	 2‐3	
6	 4	 4	 4	 4	 4	 4	 4	 4	 4	 3‐4	 4	 3	
7	 4	 4	 4	 3‐4	 4 4 4 4 4 3‐4	 3‐4	 3‐4
a	Alt.:	Alteration;	St:	Staining;	*	Staining	on	cotton;	**	Staining	on	wool.	
	
	
3.2.5.4.	Fastness	to	light	
	

It	 is	significantly	depending	on	nature	of	 the	substituents	
which	 change	 the	 electron	 density	 around	 hydrazo	 group.	
Generally	the	light	fastness	is	poor,	this	may	be	due	to	surface	
coloration.	
	
4.	Conclusion	
	

A	 series	 of	 reactive	 azo‐dyes	 were	 prepared	 through	
simple	 synthetic	 pathways	 and	 they	 applied	 to	 cotton	 and	
naylon	 fabrics	 and	 showed	 bad	 properties	 towards	 cotton	
fibers	 but	 good	dying	properties	 towards	 naylon	 fibers	were	
observed.	
	
Acknowledgements	
	

The	 authors	 wish	 to	 thank	 the	 Dyeing	 and	 Printing	
Department,	 Textile	 Division,	 National	 Research	 Center	 for	
giving	 us	 the	 chance	 to	 perform	 some	 applications	 on	 the	
prepared	dyes.	
	
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