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European	Journal	of	Chemistry	3	(3)	(2012)	322‐331	

European	Journal	of	Chemistry	
ISSN	2153‐2249	(Print)	/	ISSN	2153‐2257	(Online)		2012	EURJCHEM	

DOI:10.5155/eurjchem.3.3.322‐331.629	

	
	

	

	

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

	 	 	

Synthesis	of	5‐arylazothiazoles,	pyridines	and		
thieno[2,3‐b]pyridines	derivatives	containing	1,2,3‐triazole	moiety	

Abdou	Osman	Abdelhamid*,	Nadia	Abdelhamid	Abdel‐Riheem,		
Tamer	Tawhid	El‐Idreesy	and	Huda	Refat	Mahmoud	Rashdan	

Department	of	Chemistry,	Faculty	of	Science,	Cairo	University,	Giza,	12613,	Egypt	

*Corresponding	author	at:	Department	of	Chemistry,	Faculty	of	Science,	Cairo	University,	Giza,	12613,	Egypt.	Tel.:	+20.2.1005205750;		
fax:	+20.2.35676573.	E‐mail	address:	abdelhamid45@gmail.com	(A.O.	Abdelhamid).	

	
	

	 	

	 	 	
ARTICLE	INFORMATION	 	 ABSTRACT	
Received:	04	May	2012	
Received	in	revised	form:	25	June	2012	
Accepted:	25	June	2012	
Online:	30	September	2012	

KEYWORDS	

	 1‐(2‐(4,5‐Dihydro‐3‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐5‐phenylpyrazol‐1‐yl)‐4‐subs‐
tituted‐thiazol‐5‐yl)‐2‐phenyldiazene	(4)	and	substituted	pyridines	 (5‐12)	were	synthesized
via	 reaction	 of	 1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐3‐phenylprop‐2‐en‐1‐one	 with
hydrazonoyl	 halides	 and	 active	methylene	 compounds.	 Also,	 thieno[2,3‐b]pyridines	 (14a‐e)
were	prepared	through	reactions	of	2‐mercapto‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐
4‐phenyl‐pyridine‐3‐carbonitrile	 with	 halo	 ester	 and	 halo	 ketones,	 respectively.	 The	 newly
synthesized	derivetived	were	elucidated	by	elemental	analysis,	spectral	data	and	alternative
synthetic	routes	wherever	possobile.	

Urea		
Pyridines	
Quinazoline	
Carbamates	
5‐Arylthiazoles	
Thieno[2,3‐b]pyridines	

	
1.	Introduction	
	

The	 pharmaceutical	 importance	 of	 pyrazolines	 lies	 in	 the	
fact	 that	 they	 can	 be	 effectively	 utilized	 as	 antibacterial,	
antifungal,	 antiviral,	 antiparasitic,	 antitubercular	 and	
insecticidal	 agents	 [1‐6].	 Some	 of	 these	 compounds	 have	 also	
anti‐inflammatory,	 antidiabetic,	 anaesthetic	 and	 analgesic	
properties	[7‐9].	In	addition,	pyrazolines	have	played	a	crucial	
part	in	the	development	of	theory	in	heterocyclic	chemistry	and	
also	been	used	extensively	in	organic	synthesis	[10‐14].	On	the	
other	hand,	 thienopyrimidine	derivatives	are	characterized	by	
a	 very	 broad	 spectrum	 of	 biological	 activities	 such	 as	
antiallergic	[15],	antiatherosclerotic	[16],	antibacterial	[17‐19],	
anticancer	 [20],	 antiviral	 [21,22],	 antihypertensive	 [23,24],	
antidepressant	 [25],	 antihistaminic	 [26],	 antimicrobial	 [27‐31]	
and	 neurotropic	 [32]	 activities.	 As	 an	 extension	 of	 our	 study	
[33‐41]	and	as	a	part	of	our	program	aiming	at	the	synthesis	of	
different	 heterocyclic	 derivatives,	 we	 report	 herein	 the	
convenient	 synthesis	 of	 5‐arylazothiazoles,	 synthesis	 of	
pyridines	 and	 thienopyridine	 derivatives	 containing	 1,2,3‐
triazole	moiety	

	
2.	Experimental	
	
2.1.	Instrumentation	
	

All	 melting	 points	 were	 determined	 on	 an	 electrothermal	
apparatus	and	are	uncorrected.	IR	spectra	were	recorded	(KBr	
discs)	on	a	Shimadzu	FT‐IR	8201	PC	spectrophotometer.	1H	and	
13C	 NMR	 spectra	 were	 recorded	 in	 CDCl3	 and	 (CD3)2SO	
solutions	 on	 a	 Varian	 Gemini	 300	 MHz	 and	 JNM‐LA	 400	 FT‐
NMR	system	spectrometer	and	chemical	shifts	are	expressed	in	
	 ppm	units	using	TMS	as	an	 internal	 reference.	Mass	spectra	

were	 recorded	 on	 a	 GC‐MS	 QP1000	 EX	 Shimadzu.	 Elemental	
analyses	were	carried	out	at	the	Microanalytical	Center	of	Cairo	
University.	 Hydrazonoyl	 halides	 [42,43]	 and	 1‐(5‐methyl‐1‐
phenyl‐1H‐1,2,3‐triazol‐4‐yl)ethanone	 [44]	 were	 prepared	 as	
previously	reported.		
	
2.2.	Synthesis	
	
2.2.1.	1‐(5‐Methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐3‐
phenylprop‐2‐en‐1‐one	(1)	
	

Sodium	hydroxide	(10	mL,	10%)	was	added	dropwise	to	a	
mixture	 of	 1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)	 ethan‐
one	(2	g,	10	mmol)	and	benzaldehyde	(1	g,	10	mmol)	in	ethanol	
(20	mL)	while	stirring	at	0‐5	oC.	The	reaction	mixture	was	left	
for	2	h	then	the	resulting	solid	was	collected	and	recrystallized	
from	 ethanol	 to	 give	1	 (Scheme	 1).	 Color:	White.	 Yield:	 87%.	
M.p.:	126‐128	°C	 (M.p.:	123‐125	 oC	 [45]).	FT‐IR	(KBr,	,	 cm‐1):	
3064	(CH),	1665	 (CO),	1604	(C=N),	1574	(C=C).	 1H	NMR	(300	
MHz,	 DMSO‐d6,	 δ,	 ppm):	 2.60	 (s,	 3H,	 CH3),	 7.42‐7.44	 (m,	 3H,	
ArH's),	7.47‐7.50	(m,	2H,	ArH's),	7.75‐7.60	(m,	3H,	ArH's),	7.72‐
7.75	 (m,	 2H,	 ArH's),	 7.90‐7.96	 (d,	 1H,	 J	 =	 16	Hz,	 CH=C),	 8.10‐
8.15	(d,	1H,	J	=	16	Hz,	CH=C).	MS	(EI,	m/z	(%)):	289	(M+,	3),	233	
(60),	217	(11),	180	(25),	140	(6),	130	(53),	118	(66),	115	(25),	
103	(50),	77	(100),	51	(70).	Anal	calcd.	for	C18H15N3O:	(289.33)	
C,	74.72;	H,	5.23;	N,	14.52..	Found:	C,	74.79;	H,	5.18;	N,	14.61%.		
	
2.2.2.	3‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐5‐phenyl‐
4,5‐dihydro‐1H‐pyrazole‐1‐carbothioamide	(2)	
	

A	mixture	of	1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐3‐
phenylprop‐2‐en‐1‐one	(1)	(1.45	g,	5	mmol),	thiosemicarbazide		

	
	



Abdelhamid	et	al.	/	European	Journal	of	Chemistry	3	(3)	(2012)	322‐331	 323	
 

	

N

N

N

Ph

O Ph

R

N
N

S
NH2

Ph

R

N
N

Ph

S
N

R'
N N

Ph

R =

R

N
N

Ph

S
N

R'

R' = CH3, C6H5

i = NH2NHCSNH2
ii = CH3COCH2Cl,

C6H5COCH2Br
iii = CH3COC(Cl):NNHPh,

C6H5COC(Br):NNHPh
PhN2Cl

i ii

iii

1
2

3

4a, R' = CH3
b, R' = C6H5 	

	
Scheme	1

	
	

(0.46	 g,	 5	 mmol)	 and	 sodium	 hydroxide	 (0.5	 g,	 10	 mmol)	 in	
ethanol	 (20	mL)	was	 refluxed	 for	3	h.	The	 resulting	 solid	was	
collected	and	recrystallized	from	ethanol	to	give	2	(Scheme	1).	
Color:	White.	Yield:	82%.	M.p.:	184‐186	°C.	FT‐IR	(KBr,	,	cm‐1):	
3475,	3355(NH2),	3035	(CH),	1600	(C=N),	1562	(C=C).	1H	NMR	
(300	MHz,	DMSO‐d6,	δ,	ppm):	2.54	(s,	3H,	CH3),	3.66	(dd,	1H,	J	=	
18.1,	 5.8	 Hz,	 CH2	 (pyraz)),	 4.01	 (dd,	 1H,	 J	 =	 18.1,	 12	 Hz,	 CH2	

(pyraz)),	5.33	(dd,	1H,	J	=	12.2,	5.8	Hz	 ,	CH	(pyraz)),	7.25‐7.72	
(m,	10H,	ArH’s),	9.11	(s.	br.,	2H,	NH2).	13C	NMR	(75	MHz,	DMSO‐
d6,	δ,	ppm):	7.90	(CH3),	39.52	(CH2),	60.12	(CH),	118.35,	127.22,	
127.41,	127.80,	129.31,	129.67,	131.47,	138.36,	139.45,	142.67,	
144.44,	 178.24.	 MS	 (EI,	m/z	 (%)):	 359	 (M‐3,	 0.1),	 358	 (M‐4,	
0.2),	93	(4.4),	91	(100),	60	(59),	59	(27),	58	(8).	Anal.	calcd.	for	
C19H18N6S:	C,	62.96;	H,	5.01;	N,	23.19;	S,	8.85.	Found:	C,	63.10;	
H,	4.88;	N,	23.00;	S,	8.78%.	
	
2.2.3.	4‐(4,5‐Dihydro‐1‐(4‐substituted	thiazol‐2‐yl)‐5‐phenyl‐
1H‐pyrazol‐3‐yl)‐5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazole	(3a,	b)	
	

A	 mixture	 of	 4,5‐dihydro‐3‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)‐5‐phenyl‐pyazole‐1‐carbothioamide	 (2)	 (1.81	 g,	 5	
mmol),	 the	 appropriate	 of	 chloroacetone	 or	 ω‐bromo	
acetophenone	(5	mmol)	in	ethanol	(20	mL)	refluxes	for	3	h.	The	
resulting	solid,	after	cooling	was	collected	and	recrystallized	to	
give	3a	and	3b,	respectively	(Scheme	1).	

4‐(4,5‐Dihydro‐1‐(4‐methylthiazol‐2‐yl)‐5‐phenyl‐1H‐
pyrazol‐3‐yl)‐5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazole	 (3a):	 Color:	
Grey	crystals	from	acetic	acid.	Yield:	81%.	M.p.:	198‐200	°C.	FT‐
IR	 (KBr,	,	 cm‐1):	 3058	 (CH),	 1595	 (C=C).	 1H	NMR	 (300	MHz,	
DMSO‐d6,	δ,	ppm):	2.10	(s,	3H,	CH3),	2.54	(s,	3H,	CH3),	3.66	(dd,	
1H,	J	=	18.1,	5.8	Hz,	CH2(pyraz)),	4.01	(dd,	1H,	J	=	18.1,	12.0	Hz,	
CH2(pyraz)),	5.33	(dd,	1H,	J	=	12.2,	5.8	Hz	,	CH(pyraz)),	6.10	(s,	
1H,	thiazole	H‐5),	7.25‐7.66	(m,	10H,	ArH’s).	MS	(EI,	m/z	(%)):	
400	(M+,	19),	399	(19),	389	(16),	385	(22),	374	(21),	362	(26),	
341	(24),	322	(18),	302	(26),	279	(25),	256	(23),	244	(21),	222	
(28),	212	(48),	206	(18),	167	(27),	149	(91),	139	(19),	125	(42),	
110	(63),	95	(58).	Anal.	calcd.	for	C22H20N6S:	C,	65.98;	H,	5.03;	
N,	20.98;	S,	8.01.	Found:	C,	66.12;	H,	4.97;	N,	21.20;	S,	7.89%.	

4‐(4,5‐Dihydro‐5‐phenyl‐1‐(4‐phenylthiazol‐2‐yl)‐1H‐
pyrazol‐3‐yl)‐5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazole	 (3b):	 Color:	
Yellow	crystals	from	dioxane.	Yield:	79%.	M.p.:	250‐252	°C.	FT‐
IR	 (KBr,	,	 cm‐1):	 3058	 (CH),	 1597	 (C=C).	 1H	NMR	 (300	MHz,	
DMSO‐d6,	δ,	ppm):	2.54	(s,	3H,	CH3),	3.66	(dd,	1H,	J	=	18.1,	5.8	
Hz,	CH2(pyraz)),	4.01	(dd,	1H,	J	=	18.1,	12	Hz,	CH2(pyraz)),	5.33	
(dd,	1H,	J	=	12.2,	5.8	Hz	,	CH(pyraz)),	6.58	(s,	1H,	thiazole	H‐5),	
7.21‐7.69	 (m,	 15H,	 ArH’s).	 MS	 (EI,	m/z	 (%)):	 462	 (M+,	 0.06),	
400	 (46),	 242	 (6),	 240	 (8),	 156	 (14),	 130	 (26),	 113	 (15),	 103	
(20),	 91	 (15),	 77	 (100),	 67	 (11).	 Anal.	 calcd.	 for	 C27H22N6S:	 C,	

70.11;	 H,	 4.79;	 N,	 18.17;	 S,	 6.93.	 Found:	 C,	 70.23;	 H,	 4.92;	 N,	
17.88;	S,	7.13%.	
	
2.2.4.	1‐(2‐(4,5‐Dihydro‐3‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)‐5‐phenylpyrazol‐1‐yl)‐4‐substituted	thiazol‐5‐
yl)‐2‐phenyldiazene	(4a,	b)	
	

Method	A:	A	mixture	of	4,5‐dihydro‐3‐(5‐methyl‐1‐phenyl‐
1H‐1,2,3‐triazol‐4‐yl)‐5‐phenyl‐pyazole‐1‐carbothioamide	 (2)	
(1.81	 g,	 5	 mmol),	 the	 appropriate	 of	 hydrazonoyl	 halides	 (5	
mmol)	 and	 triethylamine	 (0.75	mL,	 0.5	 g,	 5	mmol)	 in	 ethanol	
(20	 mL)	 refluxes	 4	 h.	 The	 resulting	 solid	 was	 collected	 and	
recrystallized	to	give	4a	and	4b,	respectively	(Scheme	1).	

Method	 B:	 Benzenediazonium	 chloride	 (5	 mmol),	 which	
prepared	from	aniline	(0.45	mL,	5	mmol),	hydrochloric	acid	(6	
N,	 6	 mL),	 and	 sodium	 nitrite	 (0.35	 g,	 5	 mmol),	 was	 added	
dropwise	with	stirring	to	a	cold	solution	(0‐5	oC	)	of	a	mixture	
of	 the	 appropriate	 3a	 or	 3b	 (5	 mmol)	 and	 sodium	 acetate	
trihydrate	 (1.3	 g,	 10	mmol)	 in	 ethanol	 (50	ml).	 The	 resulting	
solid	 was	 collected	 and	 recrystallized	 to	 afford	 products	
identical	with	4a	and	4b.	

1‐(2‐(4,5‐Dihydro‐3‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐
yl)‐5‐phenylpyrazol‐1‐yl)‐4‐methylthiazol‐5‐yl)‐2‐phenyldiazene	
(4a):	Color:	Orange	crystals	 from	acetic	acid.	Yield:	82%.	M.p.:	
218‐220	 °C.	 FT‐IR	 (KBr,	 ,	 cm‐1):	 3023	 (CH),	 1597	 (C=C).	 1H	
NMR	 (300	MHz,	 DMSO‐d6,	 δ,	 ppm):	 2.44	 (s,	 3H,	 CH3),	 2.56	 (s,	
3H,	CH3),	3.61	(dd,	1H,	 J	=	18.1,	5.8	Hz,	CH2(pyraz)),	4.01	(dd,	
1H,	J	=	18.1,	12	Hz,	CH2(pyraz)),	5.32	(dd,	1H,	J	=	12.2,	5.8	Hz	,	
CH(pyraz)),	 7.21‐7.89	 (m,	 15H,	ArH’s).	MS	 (EI,	m/z	 (%)):	 505	
(M+1,	 2.8),	 504	 (M+,	 15),	 169	 (5),	 155	 (9),	 143	 (6),	 130	 (21),	
112	(14),	104	(15),	91	(13),	77	(100),	66	(11).	Anal.	calcd.	for	
C28H24N8S:	C,	66.65;	H,	4.79;	N,	22.21;	S,	6.35.	Found:	C,	66.55;	
H,	4.87;	N,	22.00;	S,	6.51%.	

1‐(2‐(4,5‐Dihydro‐3‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐
yl)‐5‐phenylpyrazol‐1‐yl)‐4‐phenylthiazol‐5‐yl)‐2‐phenyldiazene	
(4b):	Color:	Red	crystals	from	acetic	acid.	Yield:	81%.	M.p.:	246‐
248	 °C.	 FT‐IR	 (KBr,	,	 cm‐1):	 3062	 (CH),	 1601	 (C=C).	 1H	NMR	
(300	MHz,	DMSO‐d6,	δ,	ppm):	2.56	(s,	3H,	CH3),	3.61	(dd,	1H,	J	=	
18.1,	 5.8	 Hz,	 CH2(pyraz)),	 4.01	 (dd,	 1H,	 J	 =	 18.1,	 12	 Hz,	
CH2(pyraz)),	 5.32	 (dd,	 1H,	 J	 =	 12.2,	 5.8	Hz	 ,	 CH(pyraz)),	 7.09‐
8.19	(m,	20H,	ArH’s).	MS	(EI,	m/z	(%)):	566	(M+,	0.4),	174	(31),	
102	(38),	80	(100),	74	(38),	73	(13).	Anal.	calcd.	for	C33H26N8S	
(566.68)	C,	69.94;	H,	4.62;	N,	19.77;	S,	5.66.	Found:	C,	70.12;	H,	
4.75;	N,	19.62;	S,	5.81%.	
	
	
	
	



324	 Abdelhamid	et	al.	/	European	Journal	of	Chemistry	3	(3)	(2012)	322‐331	
	
	

	
	

Scheme	2
	
	
2.2.5.	6‐(5‐Methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐phenyl	
pyridine	derivatives	(5‐10)	and	pyrazolo[3,4‐b]pyridine	
(11a,	b)	
	

Method	 A:	 A	 mixture	 of	 1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)‐3‐phenylprop‐2‐en‐1‐one	(1)	(1.45	g,	5	mmol),	the	
appropriate	 ethyl	 acetoacetate,	 malononitrile,	 ethylcyano‐
acetate,	 cyanoacetamide,	 benzoylacetonitrile,	 cyanothio‐
acetamide,	 3‐methyl‐1H‐pyrazol‐5(4H)‐one or	 3‐methyl‐1‐
phenyl‐1H‐pyrazol‐5(4H)‐one	 (5	 mmol)	 and	 ammonium	
acetate	 (0.38	 g,	 5	 mmol),	 was	 heated	 in	 acetic	 acid	 (10	 mL)	
under	reflux	for	3	h.	on	cooling,	the	separated	solid	was	filtered,	
washed	with	water	and	crystallized	from	the	proper	solvent	to	
afford	5‐11a	and	11b	(Scheme	2).	

Method	 B:	 A	 mixture	 of	 1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)ethanone	 (1	 g,	 5	mmol),	 benzaldehyde	 (0.51	 g,	 (5	
mmol))	 and	 the	 appropriate	 ethyl	 acetoacetate,	malononitrile,	
ethyl	 cyanoacetate,	 cyanoacetamide,	 benzoylacetonitrile,	
cyanothioacetamide,	 3‐methyl‐1H‐pyrazol‐5(4H)‐one	 or	 3‐
methyl‐1‐phenyl‐1H‐pyrazol‐5(4H)‐one	 (5	 mmol)	 and	
ammonium	 acetate	 (4.0	 g),	 was	 heated	 in	 n‐butanol	 (10	mL)	
under	reflux	for	4	h.	on	cooling,	the	separated	yellow	solid	was	
filtered,	washed	with	water	and	recrystallized	from	the	proper	
solvent	 to	 give	 corresponding	 products	 which	 obtained	 in	
method	A.	

Ethyl	 2‐methyl‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐
4‐phenylpyridine‐3‐carboxylate	(5):	Color:	Yellow.	Crystals	from	
ethanol.	 Yield:	 69%.	 M.p.:	 188‐190	 °C.	 FT‐IR	 (KBr,	 ,	 cm‐1):	
2923,	2854	(CH),	1681	(CO),	1612	(C=N),	1570	(C=C).	1H	NMR	
(400	MHz,	DMSO‐d6,	δ,	ppm):	1.03	(t,	3H,	J	=	7,	12	Hz,	CH2CH3),	
2.22	 (s,	 3H,	 CH3),	 2.49	 (s,	 3H,	 CH3),	 4.57	 (q,	 2H,	 J	 =	 7	 Hz,	
CH2CH3),	7.11‐7.60	(m,	10H,	ArH’s),	8.35	(s,	1H,	pyridine	H‐5).	
MS	 (EI,	m/z	 (%)):	 398	M+,	 (4)),	 343	 (13),	 295	 (14),	 267	 (98),	
164	(11),	130	(24),	118	(19),	115	914),	77	(100),	65	(11).	Anal.	

calcd.	 for	 C24H22N4O2:	 C,	 72.34;	 H,	 5.57;	 N,	 14.06.	 Found:	 C,	
72.41;	H,	5.70;	N,	13.8%.	

2‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐
phenylpyridine‐3‐carbonitrile	 (6):	 Color:	 Yellow	 crystals	 from	
ethanol.	Yield:	73%.	M.p.:	224‐226	°C	[45].	FT‐IR	(KBr,	,	cm‐1):	
3465,	3502	(NH2),	2202	(CN),	1589	(C=C).	1H	NMR	(400	MHz,	
DMSO‐d6,	δ,	ppm):	2.49	(s,	3H,	CH3),	7.02	(s.	br.,	2H,	NH2),	7.41‐
7.61	 (m,	 11H,	 ArH’s).	 MS	 (EI,	m/z	 (%)):	 353	 (M+1,	 3.3),	 351	
(M+,	 29),	 324	 (93),	 281	 (11),	 247	 (13),	 220	 (48),	 194	 (11),	
17614),	 149	 (13),	 130	 (85),	 77	 (92),	 51	 (63).	 Anal.	 calcd.	 for	
C21H16N6:	C,	71.58;	H,	4.58;	N,	23.85.	Found:	C,	71.62;	H,	4.74;	N,	
23.69%.	

1,2‐Dihydro‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐2‐
oxo‐4‐phenylpyridine‐3‐carbonitrile	 (7):	 Color:	 White	 crystals	
from	 acetic	 acid.	 Yield:	 87%.	M.p.:	 250‐252	 °C.	 FT‐IR	 (KBr,	,	
cm‐1):	 3344	 (NH),	 3062	 (CH),	 2218	 (CN),	 1701	 (CO),	 1616	
(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.45	(s,	3H,	CH3),	
7.02	 ‐7.61	(m,	11H,	ArH’s	and	pyridine	H‐5),	11.65	 (s.	br.,	1H,	
NH).	MS	(EI,	m/z	(%)):	353	(M+,	27.8),	352	(M‐1,	32),	327	(91),	
269	(12),	254	(16),	221	(37),	194	(10),	176	(15),	152	(15),	130	
(69),	77	(100),	51	(55).	Anal.	calcd.	for	C21H15N5O:	C,	71.38;	H,	
4.28;	N,	19.82.	Found:	C,	71.41;	H,	4.15;	N,	20.00%.	

1,2‐Dihydro‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐2‐
oxo‐4‐phenylpyridine‐3‐carboxamide	 (8):	 Color:	 White	 crystals	
from	ethanol.	Yield:	72%.	M.p.:	230‐232	°C.	FT‐IR	(KBr,	,	cm‐1):	
3440,	3394	(NH2),	3062	(CH),	1693	(CO),	1601	(C=C).	1H	NMR	
(400	MHz,	DMSO‐d6,	 δ,	 ppm):	 2.48	 (s,	 3H,	 CH3),	 7.10‐7.62	 (m,	
13H,	ArH’s	and	pyridine	H‐5),	14.86	(s.	br.,	1H,	NH).	MS	(EI,	m/z	
(%)):	 373	 (M+,	 1.6),	 233	 (3.3),	 188	 (1.7),	 130	 (29),	 117	 (52),	
103	(7),	77	(100),	51	(50).	Anal.	calcd.	for	C21H17N5O2:	C,	67.91;	
H,	4.61;	N,	18.86.	Found:	C,	68.11;	H,	4.52;	N,	18.79%.	

6‐(5‐Methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐2,4‐diphenyl‐
pyridine‐3‐carbonitrile	 (9):	 Color:	 White	 crystals	 from	 acetic	
acid.	 Yield:	 87%.	M.p.:	 244‐246	 °C.	 FT‐IR	 (KBr,	,	 cm‐1):	 3062	



Abdelhamid	et	al.	/	European	Journal	of	Chemistry	3	(3)	(2012)	322‐331	 325	
 

(CH),	 2218	 (CN),	 1589	 (C=C).	 1H	NMR	 (400	MHz,	DMSO‐d6,	 δ,	
ppm):	2.55	(s,	3H,	CH3),	7.17‐8.42	(m,	16H,	ArH’s	and	pyridine	
H‐5).	MS	(EI,	m/z	(%)):	414	(M+1,	8),	413	(M+,	27),	385	(100),	
308	 (15),	 281	 (39),	 191	 (17),	 171	 (14),	 130	 (45),	 77	 (80),	 51	
(56).	 Anal.	 calcd.	 for	 C27H19N5:	 C,	 78.43;	 H,	 4.63;	 N,	 16.94.	
Found:	C,	78.43;	H,	4.63;	N,	16.94%.	

1,2‐Dihydro‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐
phenyl‐2‐thioxopyridine‐3‐carbonitrile	 (10):	 Color:	 Orange	
crystals	from	dioxane.	Yield:	87%.	M.p.:	244‐246	°C.	FT‐IR	(KBr,	
,	 cm‐1):	3310	 (NH),	3066	 (CH),	2218	 (CN),	1616	 (C=N),	1589	
(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.45	(s,	3H,	CH3),	
7.10‐7.69	 (m,	 11H,	 ArH’s	 and	 pyridine	H‐5),	 15.45	 (s.	 br.,	 1H,	
NH).	MS	(EI,	m/z	(%)):	371	(M+2,	2.6),	370	(M+1,	6),	369	(M+,	
22),	341	(95),	340	(82),	339	(12),	307	(12),	237	(34),	130	(56),	
77	(100),	51	(79).	Anal.	calcd.	for	C21H15N5S:	C,	68.27;	H,	4.09;	
N,	18.96;	S,	8.68.	Found:	C,	68.34;	H,	4.21;	N,	18.82;	S,	8.54%.	

3‐Methyl‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐
phenyl‐1H‐pyrazolo[3,4‐b]pyridine	(11a):	Color:	Brown	crystals	
from	benzene.	Yield:	91%.	M.p.:	168‐170	°C.	FT‐IR	(KBr,	,	cm‐

1):	 3379	 (NH),	 3062	 (CH),	 1635	 (C=N),	 1596	 (C=C).	 1H	 NMR	
(400	 MHz,	 DMSO‐d6,	 δ,	 ppm):	 2.56	 (s,	 3H,	 CH3),	 2.65	 (s,	 3H,	
CH3),	7.10‐7.75	(m,	11H,	ArH’s	and	pyridine	H‐5),	11.23	(s.	br.,	
1H,	NH).	MS	(EI,	m/z	 (%)):	366	(M+,	100),	365	(M‐1,	48),	250	
(11),	234	(13),	221	(20),	220	(14),	219	(14),	206	(15),	145	(14),	
130	(19),	118	(13),103	(15),	77	(24).	Anal.	calcd.	for	C22H18N6:	
C,	72.11;	H,	4.95;	N,	22.94.	Found:	C,	72.24;	H,	5.11;	N,	22.76%.	

3‐Methyl‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐1,4‐
diphenyl‐1H‐pyrazolo[3,4‐b]pyridine	 (11b):	 Color:	 Brown	
crystals	from	ethanol.	Yield:	89%.	M.p.:	118‐120	°C.	FT‐IR	(KBr,	
,	 cm‐1):	 3476	 (NH),	 3070	 (CH),	 1632	 (C=N),	 1603	 (C=C).	 1H	
NMR	 (400	MHz,	 DMSO‐d6,	 δ,	 ppm):	 2.65	 (s,	 3H,	 CH3),	 2.78	 (s,	
3H,	CH3),	 7.00‐7.82	 (m,	16H,	ArH’s	 and	pyridine	H‐5).	MS	 (EI,	
m/z	 (%)):	 443	 (M+1,	 29),	 442	 (M+,	 100),	 413	 (15),	 346	 (16),	
345	(41),	316	(10),	264	(24),	248	(10),	228	(58),	214	(45),	200	
(12),	196	(17),148	(16),	174	(14),	158	(14),	146	(18),	144	(18),	
131	(20),	115	(11),	77	(6),	54	(14).	Anal.	calcd.	for	C28H22N6:	C,	
76.00;	H,	5.01;	N,	18.99.	Found:	C,	76.12;	H,	5.14;	N,	18.78%.	
	
2.2.6.	2‐(5‐Methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐phenyl‐
6‐substituted	pyridine	(12a‐f)	
	

A	mixture	of	1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐3‐
phenylprop‐2‐en‐1‐one	(1)	(1.45	g,	5	mmol),	the	appropriate	1‐
(2‐oxo‐2‐substituted	ethyl)‐pyridinium	bromides	(5	mmol)	and	
ammonium	 acetate	 (0.38	 g,	 5	 mmol)	 in	 acetic	 acid	 (10	 mL)	
refluxes	for	4	h.	The	resulting	solid,	which	formed	after	cooling,	
was	 filtered,	 washed	 with	 water	 and	 crystallized	 from	 the	
proper	solvent	to	give	12a‐f	(Scheme	2).	

2‐(5‐Methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4,6‐diphenyl‐
pyridine	 (12a):	 Color:	 White	 crystals	 from	 acetic	 acid.	 Yield:	
84%.	M.p.:	 186‐188	 °C.	 FT‐IR	 (KBr,	,	 cm‐1):	 3058	 (CH),	 2931	
(CH),	1602	(C=N),	1550	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	
ppm):	2.76	(s,	3H,	CH3),	7.30‐8.12	(m,	17H,	ArH’s	and	pyridine	
H‐3	&	H‐5).	MS	(EI,	m/z	(%)):	388	(M+,	33),	387	(M‐1,	33),	361	
(33),	 373	 (47),	 360	 (88),	 359	 (100),	 256	 (47),	 227	 (17),	 158	
(17),	 130	 (50),	 129	 (67),	 85	 (133),	 77	 (33),	 69	 (33),	 61	 (36).	
Anal.	 calcd.	 for	C26H20N4:	C,	80.39;	H,	5.19;	N,	14.42.	Found:	C,	
80.39;	H,	5.19;	N,	14.42%.	

2‐(5‐Methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐phenyl‐6‐p‐
tolylpyridine	 (12b):	 Color:	 White	 crystals	 from	 acetic	 acid.	
Yield:	87%.	M.p.:	 170‐172	 °C.	FT‐IR	 (KBr,	,	 cm‐1):	3026	 (CH),	
2914	(CH),	1601	(C=N),	1549	(C=C).	1H	NMR	(400	MHz,	DMSO‐
d6,	 δ,	 ppm):	 2.34	 (s,	 3H,	 CH3),	 2.76	 (s,	 3H,	 CH3),	 7.30‐8.28	 (m,	
16H,	 ArH’s	 and	 pyridine	 H‐3	 &	 H‐5).	 MS	 (EI,	m/z	 (%)):	 403	
(M+1,	9),	402	(M+,	26),	401	(M‐1,	25),	375	(24),	374	(89),	373	
(100),	270	(30),	130	(22),	91(11),	77	(60),	51	(39).	Anal.	calcd.	
for	 C27H22N4:	 C,	 80.57;	 H,	 5.51;	 N,	 13.92.	 Found:	 C,	 80.71;	 H,	
5.36;	N,	14.00%.	

2‐(Furan‐2‐yl)‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐
4‐phenylpyridine	 (12c):	 Color:	White	 crystals	 from	acetic	 acid.	

Yield:	87%.	M.p.:	170‐172	 °C.	FT‐IR	 (KBr,	,	 cm‐1):	3026	 (CH),	
2914	(CH),	1601	(C=N),	1549	(C=C).	1H	NMR	(400	MHz,	DMSO‐
d6,	 δ,	 ppm):	 2.64	 (s,	 3H,	 CH3),	 7.32‐8.22	 (m,	 15H,	 ArH’s	 and	
pyridine	H‐3,	H‐5,	 furan	H‐3,	H‐4,	H‐5).	MS	(EI,	m/z	 (%)):	378	
(M+,	 0.02),	 360	 (100),	 289	 (5),	 283	 (15),	 256	 (34),	 179	 (15),	
202	(8),	180	(15),	130	(25),	118	(23),	103	(16),	77	(69),	64	(6).	
Anal.	calcd.	for	C24H18N4O:	C,	76.17;	H,	4.79;	N,	14.81.	Found:	C,	
76.24;	H,	4.61;	N,	14.97%.	

2‐(Benzofuran‐2‐yl)‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐
4‐yl)‐4‐phenylpyridine	(12d):	Color:	Brown	crystals	from	acetic	
acid.	 Yield:	 87%.	M.p.:	 208‐210	 °C.	 FT‐IR	 (KBr,	,	 cm‐1):	 3082	
(CH),	2920	(CH),	1604	(C=N),	1562	(C=C).	 1H	NMR	(400	MHz,	
DMSO‐d6,	 δ,	 ppm):	 2.62	 (s,	 3H,	 CH3),	 7.21‐7.59	 (m,17H,	 ArH’s	
and	pyridine	H‐3,	H‐5,	furan	H‐3)).		
MS	(EI,	m/z	 (%)):	428	 (M+,	5),	426	(M‐2,	9),	394	(7),	382	 (6),	
361	(6),	334	 (9),	306	(7),	279	(8),	262	(6),	233	 (9),	212	(16),	
190	 (12),	 185	 (11),	 181	 (14),	 175	 (9),	 167	 (6),	 155	 (16),	 149	
(10),	123	(13),	111	(10),	105	(9),	95	(16),	93	(21),	81	(34),	75	
(16),	 71	 (74),	 69	 (43),	 67	 (25).	Anal.	 calcd.	 for	 C28H20N4O:	 C,	
78.49;	H,	4.70;	N,	13.08.	Found:	C,	78.53;	H,	4.64;	N,	13.16%.	

2‐(5‐Bromobenzofuran‐2‐yl)‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)‐4‐phenylpyridine	(12e):	Color:	White	crystals	from	
acetic	acid.	Yield:	87%.	M.p.:	196‐198	 °C.	FT‐IR	(KBr,	,	 cm‐1):	
3060	(CH),	2915	(CH),	1610	(C=N),	1576	(C=C).	1H	NMR	(400	
MHz,	DMSO‐d6,	 δ,	 ppm):	 2.67	 (s,	 3H,	 CH3),	 7.12‐7.89	 (m,	 16H,	
ArH’s	and	pyridine	H‐3,	H‐5	and	furan	H‐3).	MS	(EI,	m/z	(%)):	
509	(M+,	20),	507	(M+,	22),	480	(87),	479	(100),	375	(19),	373	
(26),	293	(13),	212	(11),	200	(29),	199	(22),	164	(13),	130	(63),	
77	(63),	51	(48).	Anal.	calcd.	for	C28H19BrN4O:	C,	66.28;	H,	3.77;	
Br,	 15.75;	 N,	 11.04.	 Found:	 C,	 66.35;	 H,	 3.65;	 Br,	 15.56;	 N,	
11.13%.	

3‐(6‐(5‐Methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐phenyl‐
pyridin‐2‐yl)‐2H‐chromen‐2‐one	 (12f):	 Color:	 Beige	 crystals	
from	dioxane.	Yield:	72%.	M.p.:	264‐266	°C.	FT‐IR	(KBr,	,	cm‐

1):	3055	(CH),	2920	(CH),	1602	(C=N),	1700	(CO),	1550	(C=C).	
1H	NMR	(400	MHz,	DMSO‐d6,	 δ,	ppm):	2.63	 (s,	 3H,	CH3),	7.12‐
7.82	(m,	15H,	ArH’s	and	pyridine	H‐3),	7.95	(s,	1H,	pyridine	H‐
5),	8.78	 (s,	1H,	pyrane	H‐4).	MS	 (EI,	m/z	 (%)):	456	 (M‐2,	30),	
428	(58),	267	(20),	164	(18),	125	(15),	119	(15),	103	(22),	82	
(27),	67	 (22).	Anal.	 calcd.	 for	C29H20N4O2:	C,	 76.30;	H,	4.42;	N,	
12.27.	Found:	C,	76.42;	H,	4.34;	N,	12.10%.	
	
2.2.7.	2‐(Substituted	thio)‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)‐4‐phenylpyridine‐3‐carbonitrile	(13a‐f)	
	

A	 mixture	 of	 1,2‐dihydro‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)‐4‐phenyl‐2‐thioxopyridine‐3‐carbonitrile	 (10)	
(1.84	g,	5	mmol),	potassium	hydroxide	(0.28	g,	5	mmol)	in	N,N‐
dimethylformamide	 (10	 mL)	 was	 stirred	 for	 2h	 at	 room	
temperature.	 The	 appropriate	 of	 ethyl	 chloroacetate,	
chloroacetone,	 2‐bromo‐1‐phenylethanone,	 2‐bromo‐1‐p‐
tolylethanone,	chloroacetonitrile	or	iodomethane	(5	mmol)	was	
added	 while	 stirring.	 Stirred	 was	 continued	 for	 2h.	 The	
resulting	 solid	 was	 collected	 and	 crystallized	 to	 afford	 13a‐f,	
respectively,	(Scheme	3).	

Ethyl	 2‐(3‐cyano‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐
yl)‐4‐phenylpyridin‐2‐ylthio)acetate	 (13a):	 Color:	 Brown	
crystals	from	ethanol.	Yield:	77%.	M.p.:	138‐140	°C.	FT‐IR	(KBr,	
,	 cm‐1):	 3065	 (CH),	 2977,	 2929	 (CH),	 2114	 (CN),	 1742	 (CO),	
1587	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	1.09	(t,	3H,	
CH2CH3),	 2.62	 (s,	 3H,	 CH3),	 4.05	 (q,	 2H,	 CH2CH3),	 4.29	 (s,	 2H,	
SCH2),	7.59‐7.97	(m,	11H,	ArH’s	and	pyridine	H‐5).	MS	(EI,	m/z	
(%)):	456	(M+1,	5),	455	(M+,	18),	426	(11),	352	(33),	351	(23),	
339	(10),	250	(10),	130	(13),	77	(100),	51	(58).	Anal.	calcd.	for	
C25H21N5O2S:	C,	65.92;	H,	4.65;	N,	15.37;	S,	7.04.	Found:	C,	66.12;	
H,	4.54;	N,	15.52;	S,	7.17%.	

2‐(2‐Oxopropylthio)‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐
4‐yl)‐4‐phenylpyridine‐3‐carbonitrile	 (13b):	 Color:	 Brown	
crystals	from	ethanol.	Yield:	87%.	M.p.:	154‐156	°C.		

	
	



326	 Abdelhamid	et	al.	/	European	Journal	of	Chemistry	3	(3)	(2012)	322‐331	
	

	 	

	
	

Scheme	3
	
	

FT‐IR	 (KBr,	,	 cm‐1):	 3058	 (CH),	 2916	 (CH),	 2211	 (CN),	 1720	
(CO),	1581	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.32	(s,	
3H,	 CH3),	 2.62	 (s,	 3H,	 CH3),	 4.42	 (s,	 2H,	 SCH2),	 7.27‐7.95	 (m,	
11H,	ArH’s	and	pyridine	H‐5).	MS	(EI,	m/z	(%)):	426	(M+1,	5),	
425	(M+,	25),	424	(20),	396	(14),	382	(19),	353	(49),	251	(10),	
129	 (19),	 77	 (100),	 51	 (69).	 Anal.	 calcd.	 for	 C24H19N5OS:	 C,	
67.74;	 H,	 4.50;	 N,	 16.46;	 S,	 7.54.	 Found:	 C,	 67.91;	 H,	 4.48;	 N,	
16.64;	S,	7.41%.	

6‐(5‐Methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐2‐(2‐oxo‐2‐
phenyl‐ethylsulfanyl)‐4‐phenyl‐nicotinonitrile	 (13c):	 Color:	
White	 crystals	 from	 acetic	 acid.	 Yield:	 88%.	M.p.:	 158‐160	 °C.	
FT‐IR	 (KBr,	,	 cm‐1):	 3061	 (CH),	 2908	 (CH),	 2213	 (CN),	 1679	
(CO),	1585	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.62	(s,	
3H,	 CH3),	 4.52	 (s,	 2H,	 SCH2),	 7.27‐7.82	 (m,	 16H,	 ArH’s	 and	
pyridine	H‐5).	MS	(EI,	m/z	(%)):	489	(M+1,	2),	488	(M+,	8),	487	
(19),	457	(28),	353	(17),	130	(12.4),	77	(100),	76	(13),	51	(29).	
Anal.	calcd.	 for	C29H21N5OS:	C,	71.44;	H,	4.34;	N,	14.36;	S,	6.58.	
Found:	C,	71.23;	H,	4.45;	N,	14.61;	S,	6.72%.	

6‐(5‐Methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐2‐(2‐oxo‐2‐p‐
tolyl‐ethylsulfanyl)‐4‐phenyl‐nicotinonitrile	 (13d):	 Color:	White	
crystals	 from	 acetic	 acid.	 Yield:	 88%.	M.p.:	 208‐210	 °C.	 FT‐IR	
(KBr,	 ,	 cm‐1):	 3050	 (CH),	 2914	 (CH),	 2210	 (CN),	 1678	 (CO),	
1588	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.37	(s,	3H,	
CH3),	 2.70	 (s,	 3H,	 CH3),	 4.62	 (s,	 2H,	 SCH2),	 7.27‐7.95	 (m,	 15H,	
ArH’s	and	pyridine	H‐5).	Anal.	 calcd.	 for	C30H23N5OS:	C,	71.83;	

H,	4.62;	N,	13.96;	S,	6.39.	Found:	C,	71.95;	H,	4.57;	N,	14.15;	S,	
6.28%.	

2‐(Cyanomethylthio)‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐
4‐yl)‐4‐phenylpyridine‐3‐carbonitrile	(13e):	Color:	Gray	crystals	
from	ethanol.	Yield:	78%.	M.p.:	198‐200	°C.	FT‐IR	(KBr,	,	cm‐1):	
3062	 (CH),	 2970,	 2924	 (CH),	 2214	 (CN),	 1647(C=N),	 1585	
(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.72	(s,	3H,	CH3),	
4.42	(s,	2H,	SCH2),	7.58‐8.06	(m,	11H,	ArH’s	and	pyridine	H‐5).	
Anal.	 calcd.	 for	 C23H16N6S:	 C,	 67.63;	H,	 3.95;	N,	 20.57;	 S,	 7.85.	
Found:	C,	67.81;	H,	4.11;	N,	20.68;	S,	7.98%.	

6‐(5‐Methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐2‐(methylthio)‐
4‐phenylpyridine‐3‐carbonitrile	 (13f):	 Color:	 White	 crystals	
from	 acetic	 acid.	 Yield:	 78%.	M.p.:	 210‐212	 °C.	 FT‐IR	 (KBr,	,	
cm‐1):	 3062	 (CH),	 2923,	 2854	 (CH),	 2210	 (CN),	 1627(C=N),	
1595	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.62	(s,	6H,	
2CH3),	7.24‐7.89	(m,	11H,	ArH’s	and	pyridine	H‐5).	MS	(EI,	m/z	
(%)):	384	(M+1,	23),	383	(M‐1,	100),	171	(14),	170	(100),	168	
(20),	154	(15),	149	(18),	127	(10).	Anal.	calcd.	for	C22H17N5S:	C,	
68.91;	 H,	 4.47;	 N,	 18.26;	 S,	 8.36.	 Found:	 C,	 69.10;	 H,	 4.54;	 N,	
18.43;	S,	8.18%.	
	
2.2.8.	3‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐
4‐phenyl‐2‐substituted	thieno[2,3‐b]pyridine	derivatives	
(14a‐e)	
	



Abdelhamid	et	al.	/	European	Journal	of	Chemistry	3	(3)	(2012)	322‐331	 327	
 

A	mixture	of	the	appropriate	13a‐e	(5	mmol)	and	catalytic	
amount	of	piperidine	(5	drops)	in	ethanol	(20	mL)	refluxes	for	
1h.	 The	 resulting	 solid	 was	 collected	 and	 recrystallized	 from	
acetic	 acid	 to	 give	 thieno[2,3‐b]pyridines	 14a‐e,	 respectively,	
(Scheme	3).	

Ethyl	3‐amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐
phenylthieno[2,3‐b]pyridine‐2‐carboxylate	 (14a):	Color:	Yellow.	
Yield:	92%.	M.p.:	214‐216	°C.	FT‐IR	(KBr,	,	cm‐1):	3474,	3355	
(NH2),	3060	(CH),	2972,	2917	(CH),	1672	(CO),	1600	(C=C).	1H	
NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	1.04	(t,	3H,	CH2CH3),	2.71	(s,	
3H,	CH3),	4.22	(q,	2H,	CH2CH3),	5.81	(s.	br.,	2H,	NH2),	7.59‐7.89	
(m,	11H,	ArH’s	and	pyridine	H‐5).	MS	 (EI,	m/z	 (%)):	455	 (M+,	
16),	454	(M‐1,	63),	380	(27),	379	(31),	353	(18),	317	(14),	258	
(12),	148	(14),	139	(28),	107	(20),	76	(100),	57	(18),	51	(65).	
Anal.	calcd.	for	C25H21N5O2S:	C,	65.92;	H,	4.65;	N,	15.37;	S,	7.04.	
Found:	C,	66.12;	H,	4.56;	N,	15.42;	S,	7.17%.	

1‐(3‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐
phenylthieno[2,3‐b]pyridin‐2‐yl)ethanone	 (14b):	 Color:	 Orange.	
Yield:	71%.	M.p.:	226‐228	°C.	FT‐IR	(KBr,	,	cm‐1):	3476,	3314	
(NH2),	3056	(CH),	2918,	2885	(CH),	1720	(CO),	1590	(C=C).	1H	
NMR	 (400	MHz,	 DMSO‐d6,	 δ,	 ppm):	 2.35	 (s,	 3H,	 CH3),	 2.68	 (s,	
3H,	 CH3),	 5.80	 (s.	 br.,	 2H,	NH2),	 7.39‐7.69	 (m,	 11H,	 ArH’s	 and	
pyridine	H‐5).	MS	(EI,	m/z	(%)):	452	(M+,	100),	424	(M‐1,	95),	
395	(47),	391	(47),	353	(30),	292	(23),	248	(11),	198	(29),	196	
(13),	 177	 (16),	 130	 (64),	 77	 (92),	 51	 (67).	 Anal.	 calcd.	 for	
C24H19N5OS:	C,	67.74;	H,	4.50;	N,	16.46;	S,	7.54.	Found:	C,	67.64;	
H,	4.36;	N,	16.54;	S,	7.35%.	

(3‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐
phenylthieno[2,3‐b]pyridin‐2‐yl)(phenyl)methanone	 (14c):	
Color:	Yellow.	Yield:	86%.	M.p.:	260‐262	°C.	FT‐IR	(KBr,	,	cm‐

1):	3471,	3275	(NH2),	3052	(CH),	2919,	2851	(CH),	1712	(CO),	
1591	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.64	(s,	3H,	
CH3),	 6.22	 (s.	 br.,	 2H,	 NH2),	 7.21‐7.79	 (m,	 16H,	 ArH’s	 and	
pyridine	H‐5).	MS	 (EI,	m/z	 (%)):	487	 (M+,	 55),	486	 (M‐1,	49),	
458	(92),	229	(20),	130	(19),	77	(100),	51	(27).	Anal.	calcd.	for	
C29H21N5OS:	C,	71.44;	H,	4.34;	N,	14.36;	S,	6.58.	Found:	C,	71.52;	
H,	4.41;	N,	14.54;	S,	6.66%.	

(3‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐
phenylthieno[2,3‐b]pyridin‐2‐yl)(4‐methylphenyl)methanone	
(14d):	Color:	Yellow.	Yield:	80%.	M.p.:	262‐264	°C.	FT‐IR	(KBr,	
,	cm‐1):	3478,	3292	(NH2),	3031	(CH),	2918,	2852	(CH),	1709	
(CO),	1590	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.26	(s,	
3H,	CH3),	2.48	(s,	3H,	CH3),	5.09	(s.	br.,	2H,	NH2),	7.31‐7.94	(m,	
15H,	ArH’s	and	pyridine	H‐5).	MS	(EI,	m/z	 (%)):	501	(M+,	52),	
500	(M‐1,	41),	472	(100),	235	(17),	190	(11),	130	(14),	77	(35),	
65	(19),	51	(14).	Anal.	calcd.	for	C30H23N5OS	(501.6)	C,	71.83;	H,	
4.62;	 N,	 13.96;	 S,	 6.39.	 Found:	 C,	 71.92;	 H,	 4.51;	 N,	 14.15;	 S,	
6.52%.	

3‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐
phenylthieno[2,3‐b]pyridine‐2‐carbonitrile	(14e):	Color:	Yellow.	
Yield:	87%.	M.p.:	246‐248	°C.	FT‐IR	(KBr,	,	cm‐1):	3467,	3328	
(NH2),	2923,	2854	(CH),	2191	(CN),	1631	(C=N),	1585	(C=C).	1H	
NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.65	(s,	3H,	CH3),	5.60	(s.	br.,	
2H,	NH2),	7.51‐7.90	 (m,	11H,	ArH’s	and	pyridine	H‐5).	MS	 (EI,	
m/z	(%)):	409	(M+1,	13),	408	(M+,	54),	407	(45),	380	(91),	379	
(100),	277	(13),	190	(16),	169	(14),	130	(83),	77	(77),	51	(65).	
Anal.	 calcd.	 for	 C23H16N6S:	 C,	 67.63;	H,	 3.95;	 N,	 20.57;	 S,	 7.85.	
Found:	C,	67.75;	H,	4.12;	N,	20.42;	S,	7.96%.	
	
2.2.9.	2‐(5‐Methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐4‐phenyl‐
9‐thia‐1,5,7‐triaza‐fluorene	derivatives	(15	and	16)	
	

A	 mixture	 of	 14e	 (2	 g,	 5	 mmol)	 and	 the	 appropriate	 of	
formic	 acid	 (99%)	 or	 formamide	 (5	 mL)	 in	 N,N,‐
dimethylformamide	refluxes	for	7	h.	The	reaction	mixture	was	
poured	 onto	 ice	 (50	 g).	 The	 resulting	 solid	was	 collected	 and	
recrystallized	from	from	the	proper	solvent	to	give	15	and	16,	
respectively,	(Scheme	3).	

2‐(5‐Methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐4‐phenyl‐7H‐9‐
thia‐1,5,7‐triaza‐fluoren‐8‐one	(15):	Color:	White	crystals	 from	
N,N‐dimethylformamide.	Yield:	90%.	M.p.:	>300	°C.	FT‐IR	(KBr,	

,	 cm‐1):	 3452	 (NH),	 3047	 (CH),	 2920,	 2850	 (CH),	 1686	 (CO),	
1577	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.67	(s,	3H,	
CH3),	7.51‐8.35	(m,	12H,	ArH’s),	12.85	(s.	br.,	1H,	NH).	MS	(EI,	
m/z	(%)):	436	(M+,	18),	355	(10),	318	(15),	317	(64),	265	(11),	
264	(55),	257	(25),	235	(10),	222	(14),	221	(61),	209	(12),	194	
(54),	 193	 (100),	 153	 (14),	 98	 (19),	 83	 (16),	 67	 (15),	 55	 (34).	
Anal.	calcd.	for	C24H16N6OS:	C,	66.04;	H,	3.69;	N,	19.25;	S,	7.35.	
Found:	C,	66.15;	H,	3.75;	N,	19.37;	S,	7.22%.	

2‐(5‐Methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐4‐phenyl‐9‐thia‐
1,5,7‐triaza‐fluoren‐8‐ylamine	(16):	Color:	Brown	crystals	from	
dioxane.	Yield:	92%.	M.p.:	>300	°C.	FT‐IR	(KBr,	,	 cm‐1):	3309,	
3120	 (NH2),	 3062	 (CH),	 2923,	 2854	 (CH),	 1647	 (C=N),	 1570	
(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.63	(s,	3H,	CH3),	
6.68	(s.	br.,	2H,	NH2),	7.51‐8.11	(m,	12H,	ArH’s	and	pyridine	H‐
5).	MS	(EI,	m/z	(%)):	435	(M+,	3),	285	(9),	241	(11),	240	(38),	
151	(40),	150	(13),	91	(100),	65	(6).	Anal.	calcd.	for	C24H17N7S:	
C,	66.19;	H,	3.93;	N,	22.51;	S,	7.36.	Found:	C,	66.25;	H,	4.12;	N,	
22.37;	S,	7.43%.	
	
2.2.10.	Ethyl	N‐[2‐cyano‐6‐(5‐methyl‐1‐phenyl‐1H‐[1,2,3]	
triazol‐4‐yl)‐4‐phenyl‐thieno[2,3‐b]pyridin‐3‐yl]‐
formimidate	(17)	
	

A	mixture	of	14e	(2	g,	5	mmol)	and	triethyl	ortho‐formate	
(1.48	g,	10	mmol)	in	acetic	anhydride	(20	mL)	refluxes	for	6	h.	
The	reaction	mixture	was	poured	onto	ice	(30	g).	The	resulting	
solid	was	collected	and	recrystallized	 from	ethanol	 to	give	17	
(Scheme	3).	Color:	Brown.	Yield:	88%.	M.p.:	180‐182	°C.	FT‐IR	
(KBr,	,	 cm‐1):	 3062	 (CH),	2854	 (CH),	2206	 (CN),	 1639	 (C=N),	
1582	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	1.37	(t,	3H,	
CH2CH3),	2.58	(s,	3H,	CH3),	4.21	(q,	2H,	CH2CH3),	7.15‐7.48	(m,	
11H,	ArH’s	and	pyridine	H‐5),	8.15	(s,	1H,	CH=N).	MS	(EI,	m/z	
(%)):	464	(M+,	0.3),	297	(10),	256	(8),	150	(100),	130	(7),	120	
(6),	 105	 (13),	 104	 (15),	 76	 (6).	Anal.	 calcd.	 for	C26H20N6OS:	 C,	
67.22;	 H,	 4.34;	 N,	 18.09;	 S,	 6.90.	 Found:	 C,	 67.41;	 H,	 4.43;	 N,	
17.79;	S,	6.82%.	
	
2.2.11.	8‐Chloro‐2‐(5‐methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐
yl)‐4‐phenyl‐9‐thia‐1,5,7‐triaza‐fluorene	(18)	
	

A	 mixture	 of	 15	 (2.18	 g,	 5	 mmol)	 and	 phosphorus	
oxychloride	(20	mL)	refluxes	for	5	h.	The	reaction	mixture	was	
cooled	 and	 poured	 onto	 ice	 (50	 g).	 The	 resulting	 solid	 was	
collected	 and	 recrystallized	 from	 acetic	 acid	 to	 afford	 18	
(Scheme	3).	Color:	Yellow.	Yield:	96%.	M.p.:	240‐242	°C.	FT‐IR	
(KBr,	,	 cm‐1):	3056	(CH),	2920,	2850	(CH),	1647	(C=N),	1585	
(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.62	(s,	3H,	CH3),	
7.15‐7.77	 (m,	 11H,	 ArH’s	 and	 pyridine	 H‐5),	 8.68	 (s,	 1H,	
pyrimidine	H‐2).	MS	 (EI,	m/z	 (%)):	456	 (M+2,	0.03),	454	 (M+,	
0.1),	370	(10),	369	(36),	354	(100),	353	(54),	263	(31),	262	(8),	
248	(11),	247	(7.6),	236	(27),	233	(23),	221	(13),	177	(11),	118	
(21),	106	(12),	77	(31),	51	(5).	Anal.	 calcd.	 for	C24H15ClN6S:	C,	
63.36;	 H,	 3.32;	 Cl,	 7.79;	 N,	 18.47;	 S,	 7.05.	 Found:	 C,	 63.12;	 H,	
3.23;	Cl,	7.87;	N,	18.37;	S,	7.11%.	
	
2.2.12.	8‐Azido‐2‐(5‐methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐
4‐phenyl‐9‐thia‐1,5,7‐triaza‐fluorene	(19)	
	

A	mixture	of	18	(2.77	g,	5	mmol)	and	sodium	azide	(0.65	g,	
19	 mmol)	 in	 N,N‐dimethylformamide	 was	 stirred	 at	 room	
temperature	for	2h.	Then,	poured	onto	ice‐cold	water	(50	mL).	
The	 resulting	 solid	 was	 collected	 and	 recrystallized	 from	
ethanol	to	give	19	(Scheme	3).	Color:	Brown.	Yield:	96%.	M.p.:	
>300	°C.	FT‐IR	(KBr,	,	cm‐1):	3055	(CH),	2920,	2854	(CH),	2044	
(N3)	[46],	1658	(C=N),	1543	(C=C).	1H	NMR	(400	MHz,	DMSO‐
d6,	 δ,	 ppm):	 2.62	 (s,	 3H,	 CH3),	 7.15‐7.82	 (m,	 11H,	 ArH’s	 and	
pyridine	 H‐5),	 8.68	 (s,	 1H,	 pyrimidine	 H‐2).	 Anal.	 calcd.	 for	
C24H15ClN6S:	C,	62.46;	H,	3.28;	N,	27.32;	S,	6.95.	Found:	C,	62.52;	
H,	3.31;	N,	27.46;	S,	7.17%.	
	
	



328	 Abdelhamid	et	al.	/	European	Journal	of	Chemistry	3	(3)	(2012)	322‐331	
	
	

NR S

O
NH2

O NR S

HN
NH2

O

NH2

NR S

N3
NH2

O

NR S

O
NH2

N

N

CH3

X

NR S

O
NH2

N

N

CH3

X

N
N PhNR S

NH

NH2

NH

O

R'

NR S
N
H

NH2

O

O

R''

N
NH

Ph

Y
H3C

O

14a 22
23

24

25

2627

NR S
N

NH2

28

NH
O

O

29

+ 22

27a, R' = C6H5
b, R' = 4-CH3C6H4
c, R' = 4-CH3OC6H4
d, R' = 5-phenylpyrazol-3-yl

29a, R'' = C6H5
29b, R'' = 4-O2NC6H4
29c, R'' = 2,4,6- (O2N)3C6H2

R = 5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl

23, 24a, X = OH
23, 24b, X = CH3

25a, Y = CO2C2H5
25b, Y = COCH3

Ph Ph Ph

Ph Ph

Ph

Ph

Ph

	
	

Scheme	4
	
	
2.2.13.	[2‐(5‐Methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐4‐
phenyl‐9‐thia‐1,5,7‐triaza‐fluoren‐8‐yl]‐hydrazine	(20)	
	

A	mixture	of	18	(2.18	g,	5	mmol)	and	hydrazine	hydrate	(1	
g,	20	mmol)	 in	ethanol	(20	mL)	refluxes	for	3	h.	The	resulting	
solid	was	 collected	 and	 recrystallized	 from	 acetic	 acid	 to	 give	
20	(Scheme	3).	Color:	Yellow.	Yield:	96%.	M.p.:	240‐242	°C.	FT‐
IR	(KBr,	,	cm‐1):	3388,	3337,	3217	(NH,	NH2),	3062	(CH),	2920,	
2851	(CH),	1645	(C=N),	1551	(C=C).	1H	NMR	(400	MHz,	DMSO‐
d6,	 δ,	 ppm):	 2.62	 (s,	 3H,	CH3),	6.25	 (s.	 br.,	 3H,	NH,	NH2),	 7.15‐
7.77	(m,	11H,	ArH’s	and	pyridine	H‐5),	8.68	(s,	1H,	pyrimidine	
H‐2).	MS	(EI,	m/z	 (%)):	450	(M+,	4),	332	(20),	331	(100),	238	
(54),	174	(12),	160	(64),	155	(62),	94	(12),	93	(35),	91	(54),	84	
(17),	65	(8),	56	(9).	Anal.	calcd.	for	C24H18N8S:	C,	63.98;	H,	4.03;	
N,	24.87;	S,	7.12.	Found:	C,	64.12;	H,	4.11;	N,	24.94;	S,	7.23%.	
	
2.2.14.	8‐(5‐Methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐6‐
phenyl‐10‐thia‐1,2,3,3a,5,9‐hexaaza‐cyclopenta[a]fluorene	
(21)	
	

Saturated	 solution	 of	 sodium	 nitrite	 (10	 mL)	 was	 added	
while	stirring	to	a	cold	solution	at	0	oC	of	20	(2.25	g,	5	mmol)	in	
acetic	 acid	 (30	 mL).	 The	 reaction	 was	 stirred	 for	 1h.	 The	
resulting	solution	was	collected	and	recrystallized	 from	acetic	
acid	gave	21	(Scheme	3).	Color:	Brown.	Yield:	89%.	M.p.:	>300	
°C.	 FT‐IR	 (KBr,	 ,	 cm‐1):	 3070	 (CH),	 2920,	 2850	 (CH),	 1625	
(C=N),	1585	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.64	

(s,	3H,	CH3),	7.15‐7.68	 (m,	11H,	ArH’s	and	pyridine	H‐5),	8.48	
(s,	 1H,	 pyrimidine	 H‐2).	 MS	 (EI,	m/z	 (%)):	 461	 (M+,	 6),	 360	
(100),	 289	 (23),	 260	 (39),	 248	 (23),	 232	 (81),	 220	 (15),	 202	
(20),	189	(75),	178	(10),	174	(55),	155	(29),	148	(45),	136	(51),	
97	(12),	91	(77),	43	(19).	Anal.	calcd.	for	C24H15N9S:	C,	62.46;	H,	
3.28;	 N,	 27.32;	 S,	 6.95.	 Found:	 C,	 62.61;	 H,	 3.37;	 N,	 27.28;	 S,	
7.11%.	
	
2.2.15.	3‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐
4‐phenylthieno[2,3‐b]pyridine‐2‐carbohydrazide	(22)	
	

A	mixture	of	ethyl	3‐amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)‐4‐phenylthieno[2,3‐b]pyridine‐2‐carboxylate	
(14a)	 (2.27	 g,	 5	mmol)	 and	 hydrazine	 hydrate	 (1g,	 1	mL,	 10	
mmol)	in	ethanol	(20	mL)	refluxes	for	1h.	The	solid	formed	was	
collected	and	recrystallized	from	ethanol	afforded	22	(Scheme	
4).	 Color:	 Yellow.	Yield:	 82%.	M.p.:	 230‐232	 °C.	 FT‐IR	 (KBr,	,	
cm‐1):	3483,	3359,	3267	(NH,	NH2),	3062(CH),	2920,	2854	(CH),	
1659	(CO),	1593	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	
2.56	(s,	3H,	CH3),	5.88	(s.	br.,	5H,	NH,	2NH2),	7.10‐7.60	(m,	11H,	
ArH’s	 and	pyridine	H‐5).	MS	 (EI,	m/z	 (%)):	 441	 (M+,	49),	 426	
(24),	289	(23),	260	(39),	248	(23),	232	(81),	220	(15),	202	(20),	
189	(75),	178	(10),	174	(55),	155	(29),	148	(45),	380	(29),	353	
(36),	312	(24),	249	(22),	191	(38),	149	(76),	77	(100),	51	(76).	
Anal.	calcd.	for	C23H19N7OS:	C,	62.57;	H,	4.34;	N,	22.21;	S,	7.26.	
Found:	C,	62.75;	H,	4.24;	N,	22.141;	S,	7.356%.	
	



Abdelhamid	et	al.	/	European	Journal	of	Chemistry	3	(3)	(2012)	322‐331	 329	
 

2.2.16.	(3‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐
yl)‐4‐phenylthieno[2,3‐b]pyridin‐2‐yl)(5‐substituted	3‐
methyl‐1H‐pyrazol‐1‐yl)methanone	dervatives	(23a	and	b)	
	

A	 mixture	 of	 3‐amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)‐4‐phenylthieno[2,3‐b]pyridine‐2‐carbohydrazide	
(22)	 (2.2	 g,	 5	 mmol),	 ethyl	 acetoacetate	 or	 acetylacetone	 in	
ethanol	 (20	mL)	and	acetic	acid	 (5	drops)	 refluxes	 for	3	h.	on	
cooling,	 the	 separated	 yellow	 solid	 was	 filtered,	washed	with	
water	and	crystallized	 from	acetic	acid	 to	afford	23a	and	23b	
(Scheme	4).	

2‐[3‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐4‐
phenyl‐thieno[2,3‐b]pyridine‐2‐carbonyl]‐5‐methyl‐2,4‐dihydro‐
pyrazol‐3‐one	 (23a	 ):	Color:	Brown.	Yield:	89%.	M.p.:	180‐182	
°C.	 FT‐IR	 (KBr,	 ,	 cm‐1):	 3479,	 3325	 (NH2),	 3062	 (CH),	 2924,	
2855	 (CH),	 1724,	 1674	 (CO),	 1593	 (C=C).	 1H	NMR	 (400	MHz,	
DMSO‐d6,	δ,	ppm):	2.12	(s,	3H,	CH3),	2.57	(s,	3H,	CH3),	4.31	(dd,	
1H,	CH2,	 ,	pyrazolole),	3.56	(dd,	1H,	CH2,	pyrazole),	6.77	(s.	br.,	
2H,	NH2),	7.12‐7.74	 (m,	11H,	ArH’s	and	pyridine	H‐5).	MS	 (EI,	
m/z	 (%)):	 507	 (M+,	 10),	 450	 (18),	 449	 (28),	 448	 (100),	 390	
(13),	274	(16).	Anal.	calcd.	for	C27H21N7O2S:	C,	63.89;	H,	4.17;	N,	
19.32;	S,	6.32.	Found:	C,	64.00;	H,	4.05;	N,	19.45;	S,	6.48%.	

3‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐4‐
phenyl‐thieno[2,3‐b]pyridin‐2‐yl]‐(3,5‐dimethyl‐pyrazol‐1‐yl)‐
methanone	(23b):	Color:	Brown.	Yield:	89%.	M.p.:	218‐220	°C.	
FT‐IR	(KBr,	,	cm‐1):	3479,	3325	(NH2),	3062	(CH),	2923,	2855	
(CH),	1670	(CO),	1627	(C=N),	1593	 (C=C).	 1H	NMR	(400	MHz,	
DMSO‐d6,	δ,	ppm):	2.28	(s,	3H,	CH3),	2.38	(s,	3H,	CH3),	2.59	(s,	
3H,	CH3),	5.52	(s,	1H,	pyrazole	H‐4),	6.55	(s.	br.,	2H,	NH2),	7.12‐
7.79	 (m,	11H,	ArH’s	and	pyridine	H‐5).	MS	 (EI,	m/z	 (%)):	505	
(M+,	3.6),	503	(14),	465	(9),	448	(41),	406	(21),	331	(39),	220	
(7),	206	(10),	178	(27),	169	(78),	136	(23),	135	(23),	127	(14),	
109	 (24),	 43	 (100).	 Anal.	 calcd.	 for	 C28H23N7OS:	 C,	 66.52;	 H,	
4.59;	 N,	 19.39;	 S,	 6.34.	 Found:	 C,	 66.45;	 H,	 4.48;	 N,	 19.28;	 S,	
6.52%.	
	
2.2.17.	2‐[3‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐
yl)‐4‐phenyl‐thieno[2,3‐b]pyridine‐2‐carbonyl]‐5‐methyl‐4‐
(phenyl‐hydrazono)‐2,4‐dihydro‐pyrazol‐3‐one	(24a)	and	
[3‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐4‐
phenyl‐thieno[2,3‐b]pyridin‐2‐yl]‐(3,5‐dimethyl‐4phenylazo‐
pyrazol‐1‐yl)‐methanone	(24b)		
	

Method	 A:	 Benzenediazonium	 chloride	 (5	 mmol),	 which	
was	 prepared	 via	 reaction	 of	 aniline	 (0.46	 g.	 5	 mmol),	
hydrochloric	 acid	 (3	mL,	 6	M)	 and	 sodium	nitrite	 (0.37	 gm,	5	
mmole)	 at	 0‐5	 °C,	was	 added	 to	 a	mixture	 of	 the	 appropriate	
23a	or	32b	(5	mmole)	and	sodium	acetate	(0.41	g,	5	mmole)	in	
ethanol	(30	mL)	at	0‐5	°C,	while	stirring.	The	reaction	mixture	
was	stirred	 for	3	h.	The	resulting	solid,	was	collected,	washed	
with	water	and	recrystallized	from	acetic	acid	to	give	24a	and	
24b,	respectively,	(Scheme	4).	

Method	 B:	 A	 mixture	 of	 22a	 (2.2	 g,	 5	 mmol)	 and	 the	
appropriate	of	ethyl	2‐(2‐phenylhydrazono)‐3‐oxobutanoate	or	
3‐(2‐phenyl‐hydrazono)pentane‐2,4‐dione	(5	mmol)	in	ethanol	
(20	 mL)	 and	 catalytic	 amount	 of	 acetic	 acid	 (2	 drops)	 was	
refluxed	 for	 2	h.	 The	 resulting	 solid,	 so	 formed,	was	 collected	
and	recrystallized	from	acetic	acid	to	give	products	identical	in	
all	aspects	to	those	obtained	from	method	A.	

2‐[3‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐4‐
phenyl‐thieno[2,3‐b]pyridine‐2‐carbonyl]‐5‐methyl‐4‐(phenyl‐
hydrazono)‐2,4‐dihydro‐pyrazol‐3‐one	 (24a):	 Color:	 Brown.	
Yield:	92%.	M.p.:	208‐210	°C.	FT‐IR	(KBr,	,	cm‐1):	3479,	3359,	
3325	(NH,	NH2),	3066	(CH),	2920	(CH),	1678,	1647	(CO),	1605	
(C=N),	1550	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.10	
(s,	 3H,	 CH3),	 2.62	 (s,	 3H,	 CH3),	 6.89‐7.72	 (m,	 16H,	 ArH’s	 and	
pyridine	H‐5),	9.42	(s.	br.,	3H,	NH,	NH2).	MS	(EI,	m/z	(%)):	611	
(M+,	0.2),	373	(6),	355	(100),	313	(9),	256	(10),	240	(17),	239	
(96),	227	(12),	171	(47),	159	(14),	158	(23),	117	(26),	112	(14),	
98	(34),	95	(13),	83	(24),	73	(13),	69	(26)57	(55),	43	(57).	Anal.	

calcd.	 for	 C33H25N9O2S:	 C,	 64.80;	 H,	 4.12;	 N,	 20.61;	 S,	 5.24.	
Found:	C,	64.92;	H,	4.00;	N,	20.75;	S,	5.35%.	

(3‐amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐
phenylthieno[2,3‐b]pyridin‐2‐yl)(3,5‐dimethyl‐4‐(phenyldiazen‐
yl)‐1H‐pyrazol‐1‐yl)methanone	 (24b):	 Color:	 Brown.	 Yield:	
88%.	M.p.:	240‐242	°C.	FT‐IR	(KBr,	,	cm‐1):	3614,	3568	(NH2),	
3058	 (CH),	 2916,	 2850	 (CH),	 1693	 (CO),	 1608	 (C=N),	 1550	
(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.18	(s,	3H,	CH3),	
2.28	(s,	3H,	CH3),	2.61	(s,	3H,	CH3),	6.78	(s.	br.,	2H,	NH2),	7.12‐
7.99	(m,	16H,	ArH’s	and	pyridine	H‐5).	MS	(EI,	m/z	 (%)):	609	
(M+,	35),	608	(100),	607	(45),	593	(11),	397	(29),	396	(29),	381	
(25),	 365	 (12),	 214	 (11),	 212	 (20),	 195	 (20).	 Anal.	 calcd.	 for	
C34H27N9OS:	C,	66.98;	H,	4.46;	N,	20.68;	S,	5.26.	Found:	C,	67.11;	
H,	4.34;	N,	20.88;	S,	5.14%.	
	
2.2.18.	(3‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐
yl)‐4‐phenylthieno[2,3‐b]pyridin‐2‐yl)azidomethanone	(26)	
	

A	stirred	solution	of	22	(2.2	g,	5	mmol)	in	hydrochloric	acid	
(15	mL,	6	M)	at	0‐5	°C,	sodium	nitrite	was	added	portionwise	
tell	effervescence	ended.	The	reaction	mixture	was	stirred	for	1	
h.	 The	 resulting	 solid,	 was	 collected,	 filtered,	 washed	 with	
water	and	recrystallized	from	acetic	acid	to	give	26	(Scheme	4).	
Color:	Beige.	Yield:	88%.	M.p.:	190‐192	°C.	FT‐IR	(KBr,	,	cm‐1):	
3479,	3325	 (NH2),	 3031	 (CH),	 2920	 (CH),	 2124	 (Azide),	 1678	
(CO),	1596	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.61	(s,	
3H,	 CH3),	 6.65	 (s.	 br.,	 2H,	NH2),	 7.12‐7.85	 (m,	 11H,	 ArH’s	 and	
pyridine	H‐5).	MS	(EI,	m/z	(%)):	455	(M+1,	18),	454	(16),	440	
(41),	380	(38),	354	(22),	324	(19),	286	(19),	265	(45),	239	(25),	
220	(41),	205	(38),	189	(31),	161	(34),	134	(44),	128	(47),	98	
(53),	91	 (16),	82	 (100),	77	 (41),	64	 (25),	51	 (28).	Anal.	 calcd.	
for	 C23H16N8OS:	 C,	 61.05;	 H,	 3.56;	 N,	 24.76;	 S,	 7.09.	 Found:	 C,	
61.12;	H,	3.42;	N,	24.61;	S,	7.00%.	
	
	2.2.19.	Urea	derivatives	(27a‐d)	
	

A	mixture	of	appropriate	aniline,	p‐toluidine,	p‐anisidine	or	
3‐amino‐5‐phenylpyrazole	 (5	mmol)	 and	 azido	 compound	26	
(2.26	g,	5	mmol)	 in	dry	dioxane	(20	mL)	refluxes	 for	4	h.	The	
resulting	 solid,	 so	 formed,	was	 collected	 and	 recrystallized	 to	
give	27a‐d,	respectively,	(Scheme	4).	

1‐(3‐amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐
4‐phenylthieno[2,3‐b]pyridin‐2‐yl)‐3‐phenylurea	 (27a):	 Color:	
Brown	crystals	from	ethanol.	Yield:	78%.	M.p.:	240‐242	°C.	FT‐
IR	(KBr,	,	cm‐1):	3614,	3568	(NH2),	3031	(CH),	2920(CH),	1678	
(CO),	1596	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.54	(s,	
3H,	CH3),	7.12‐7.66	(m,	20H,	ArH’s,	pyridine	H‐5,	2NH,	NH2).	MS	
(EI,	m/z	(%)):	517	(M+,	0.2),	309	(100),	280	(18),	231	(7),	208	
(18),	 204	 (14),	 206	 (24),	 128	 (15),	 105	 (41),	 77	 (19).	 Anal.	
calcd.	for	C29H23N7OS:	C,	67.29;	H,	4.48;	N,	18.94;	S,	6.19.	Found:	
C,	67.29;	H,	4.48;	N,	18.94;	S,	6.19%.	

1‐(3‐amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐
4‐phenylthieno[2,3‐b]pyridin‐2‐yl)‐3‐p‐tolylurea	 (27b):	 Color:	
Brown	crystals	from	ethanol.	Yield:	87%.	M.p.:	208‐210	°C.	FT‐
IR	 (KBr,	 ,	 cm‐1):	 3429,	 3568	 (NH2),	 3066	 (CH),	 2924,	 2823	
(CH),	1685	(CO),	1604	(C=N),	1551	(C=C).	 1H	NMR	(400	MHz,	
DMSO‐d6,	δ,	ppm):	2.25	(s,	3H,	CH3),	2.58	(s,	3H,	CH3),	7.12‐7.99	
(m,	19H,	ArH’s	and	pyridine	H‐5,	2H,	NH2).	MS	 (EI,	m/z	 (%)):	
531	(M+,	38),	530	(100),	516	(18),	515	(49),	219	(31),	203	(12),	
189	(10),	147	(15),	67	(13),	83	(15),	71	(12),	69	(18),	57	(57),	
43	(22).	Anal.	calcd.	for	C30H25N7OS:	C,	67.78;	H,	4.74;	N,	18.44;	
S,	6.03.	Found:	C,	67.87;	H,	4.7456;	N,	18.22;	S,	6.	14%.	

1‐(3‐amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐
4‐phenylthieno[2,3‐b]pyridin‐2‐yl)‐3‐(4‐methoxyphenyl)urea	
(27c):	Color:	Beige	crystals	 from	acetic	acid.	Yield:	89%.	M.p.:	
140‐142	°C.	FT‐IR	(KBr,	,	cm‐1):	3614,	3568	(NH2),	2923,	2854	
(CH),	 1653	 (CO),	 1600	 (C=C).	 1H	NMR	 (400	MHz,	DMSO‐d6,	 δ,	
ppm):	2.61	(s,	3H,	CH3),	3.65	(s,	3H,	OCH3),	7.12‐7.99	(m,	19H,	
ArH’s	and	pyridine	H‐5),	NH2,	2NH).	MS	(EI,	m/z	(%)):	547	(M+,	
2.7),	305	(5),	304	(33),	303	(100),	273	(6),	195	(6),	117	(9),	81	



330	 Abdelhamid	et	al.	/	European	Journal	of	Chemistry	3	(3)	(2012)	322‐331	
	
(6).	Anal.	calcd.	 for	C30H25N7O2S:	C,	65.80;	H,	4.60;	N,	17.90;	S,	
5.86.	Found:	C,	65.98;	H,	4.51;	N,	18.12;	S,	5.64%.	

1‐(3‐amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐
4‐phenylthieno[2,3‐b]pyridin‐2‐yl)‐3‐(3‐phenyl‐1H‐pyrazol‐5‐
yl)urea	 (27d):	 Color:	 Brown	 crystals	 from	 acetic	 acid.	 Yield:	
88%.	M.p.:	240‐242	°C.	FT‐IR	(KBr,	,	cm‐1):	3433,	3394	(NH2),	
2974,	 2939	 (CH),	 1647	 (CO),	 1550	 (C=C).	 1H	NMR	 (400	MHz,	
DMSO‐d6,	δ,	ppm):	2.61	(s,	3H,	CH3),	5.23	(s,	1H,	pyrazole	H‐4),	
7.12‐7.99	 (m,	 16H,	 ArH’s	 and	 pyridine	 H‐5),	 9.26	 (s.	 br.,	 5H,	
3NH,	NH2).	MS	(EI,	m/z	(%)):	583	(M+,	65),	300	(34),	299	(100),	
288	(12),	287	(17),	286	(78),	241	(11),	239	(15.19),	211	(18),	
197	(7),	106	(6),	79	(4),	44	(31).	Anal.	calcd.	for	C32H25N9OS:	C,	
65.85;	 H,	 4.32;	 N,	 21.60;	 S,	 5.49.	 Found:	 C,	 65.99;	 H,	 4.16;	 N,	
21.72;	S,	5.55%.	
	
2.2.20.	3‐(3‐Amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐
yl)‐4‐phenylthieno[2,3‐b]pyridin‐2‐yl)quinazoline‐
2,4(1H,3H)‐dione	(28)	
	

A	mixture	of	appropriate	methyl	anthranilate	or	anthranilic	
acid	(5	mmol)	and	azido	compound	26	(2.26	g,	5	mmol)	in	dry	
dioxane	(20	mL)	refluxes	for	4	h.	The	resulting	solid,	so	formed,	
was	 collected	 and	 recrystallized	 from	 ethanol	 to	 give	 28	
(Scheme	 4).	 Color:	 Brown.	 Yield:	 93.6%.	M.p.:	 >300	 °C.	 FT‐IR	
(KBr,	,	 cm‐1):	 3433,	 3394,	 3179	 (NH,	 NH2),	 3062	 (CH),	 2923	
(CH),	 1681	 (CO),	 1600	 (C=C).	 1H	NMR	 (400	MHz,	DMSO‐d6,	 δ,	
ppm):	2.62	(s,	3H,	CH3),	926	(s.	br.,	2H,	NH2),	7.14‐7.99	(m,	15H,	
ArH’s	 and	 pyridine	 H‐5),	 10.55	 (s.	 br.,	 1H,	 NH).	 MS	 (EI,	m/z	
(%)):	544	 (M+,	2.7),	305	 (5),	303	 (100),	227	 (8),	 126	 (9),	117	
(9),	 81	 (6).	 Anal.	 calcd.	 for	 C30H21N7O2S:	 C,	 66.28;	 H,	 3.89;	 N,	
18.04;	S,	5.90.	Found:	C,	66.12;	H,	3.979;	N,	1800;	S,	6.10%.	

	
2.2.21.	Aryl	carbamates	(29a‐c)		
	

A	 mixture	 of	 26	 (2.26	 g,	 5	 mmol)	 and	 the	 appropriate	
phenol,	 4‐nitrophenol	 or	 picric	 acid	 (5	mmol)	 in	 dry	 benzene	
(20	mL)	 refluxes	 for	 4	 h.	 The	 resulting	 solid,	 so	 formed,	 was	
collected	 and	 recrystallized	 from	 ethanol	 to	 give	 29a‐c,	
respectively,	(Scheme	4).		

Phenyl	 3‐amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐
4‐phenylthieno[2,3‐b]pyridin‐2‐ylcarbamate	 (29a):	 Color:	
Brown.	Yield:	73%.	M.p.:	226‐228	°C.	FT‐IR	(KBr,	,	cm‐1):	3271,	
3190	 (NH2),	 3062	 (CH),	 2974,	 2939	 (CH),	 1700	 (CO),	 1627	
(C=N),	1593	(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.62	
(s,	 3H,	 CH3),	 5.23	 (s,	 1H,	 pyrazole	 H‐4),	 6.88‐7.89	 (m,	 18H,	
ArH’s,	pyridine	H‐5,	NH,	NH2).	MS	(EI,	m/z	(%)):	518	(M+,	0.1),	
310	(31),	308	(100),	280	(18),	265	(5),	208	(18),	204	(14),	203	
(24),	202	(20),	154	(9),	128	(15),	105	(41),	77	(18).	Anal.	calcd.	
for	C29H22N6O2S:	 C,	 67.17;	H,	 4.28;	N,	16.21;	 S,	 6.18.	 Found:	C,	
67.17;	H,	4.28;	N,	16.21;	S,	6.18%.	

4‐Nitrophenyl	 3‐amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)‐4‐phenylthieno[2,3‐b]pyridin‐2‐ylcarbamate	 (29b):	
Color:	 Yellow.	 Yield:	 79%.	M.p.:	 >300	 °C.	 FT‐IR	 (KBr,	,	 cm‐1):	
3352	 (NH),	 3059	 (NH2),	 2922,	 2854	 (CH),	 1667	 (CO),	 1594	
(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.63	(s,	3H,	CH3),	
7.15‐7.66	(m,	16H,	ArH’s,	pyridine	H‐5,	NH,	NH2),	8.30‐8.32	(d,	
2H,	J	=	8	Hz,	ArH's).	MS	(EI,	m/z	(%)):	564	(M+1,	7),	551	(16),	
548	(6),	533	(9),	494	(7),	478	(10),	463	(10),	419	(7),	400	(5),	
382	(7),	363	(11),	323	(12),	273	(12),	239	(13),	218	(10),	197	
(10),	179	(11),	155	(13),	138	(20),	123	(22),	113	(19),	111	(38),	
97	(15),	93	(31),	86	(14),	62	(33).	Anal.	calcd.	for	C29H21N7O4S:	
C,	61.80;	H,	3.76;	N,	17.40;	S,	5.69.	Found:	C,	61.80;	H,	3.76;	N,	
17.40;	S,	5.69%.	

2,4,6‐Trinitrophenyl	3‐amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)‐4‐phenylthieno[2,3‐b]pyridin‐2‐ylcarbamate	 (29c):	
Color:	 Yellow.	 Yield:	 74%.	M.p.:	 >300	 °C.	 FT‐IR	 (KBr,	,	 cm‐1):	
3352	 (NH),	 3059	 (NH2),	 2922,	 2854	 (CH),	 1667	 (CO),	 1594	
(C=C).	1H	NMR	(400	MHz,	DMSO‐d6,	δ,	ppm):	2.62	(s,	3H,	CH3),	
7.15‐7.89	 (m,	14H,	ArH’s,	 pyridine	H‐5,	NH,	NH2),	 9.14	 (s,	 2H,	
ArH's).	MS	(EI,	m/z	(%)):	653	(M+,	0.1),	460	(10),	445	(13),	255	

(9),	 216	 (5),	 122	 (7),	 105	 (100),	 77	 (24).	 Anal.	 calcd.	 for	
C29H19N9O8S:	 C,	 53.29;	 H,	 2.93;	 N,	 19.29;	 S,	 4.91.	 Found:	 C,	
53.42;	H,	3.12;	N,	19.419;	S,	5.00%.	
	
3.	Results	and	discussion	
	

Treatment	 of	 1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐
3‐phenyl‐prop‐2‐en‐1‐one	 (1)	 with	 thiosemicarbazide	 in	
boiling	 ethanolic	 sodium	 hydroxide	 gave	 4,5‐dihydro‐3‐(5‐
methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐5‐phenyl‐pyazole‐1‐
carbothioamide	(2).	Compound	2	reacted	with	the	appropriate	
hydrazonoyl	 halides	 in	 boiling	 ethanol	 containing	 catalytic	
amount	of	triethylamine	gave	1‐(2‐(4,5‐dihydro‐3‐(5‐methyl‐1‐
phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐5‐phenylpyrazol‐1‐yl)‐4‐methyl‐
thiazol‐5‐yl)‐2‐phenyldiazene	(4a)	and	1‐(2‐(4,5‐dihydro‐3‐(5‐
methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐5‐phenylpyrazol‐1‐yl)‐
4‐phenylthiazol‐5‐yl)‐2‐phenyldiazene	 (4b),	 respectively	
(Scheme	1).		

Structures	 4a	 and	 4b	 were	 confirmed	 by	 elemental	
analyses,	 spectral	data,	 and	alternative	synthetic	 routes.	Thus,	
benzenediazonium	 chloride	 reacted	 with	 each	 of	 4‐(4,5‐
dihydro‐1‐(4‐methylthiazol‐2‐yl)‐5‐phenyl‐1H‐pyrazol‐3‐yl)‐5‐
methyl‐1‐phenyl‐1H‐1,2,3‐triazole	 (3a)	 and	 4‐(4,5‐dihydro‐5‐
phenyl‐1‐(4‐phenylthiazol‐2‐yl)‐1H‐pyrazol‐3‐yl)‐5‐methyl‐1‐
phenyl‐1H‐1,2,3‐triazole	(3b),	which	prepared	via	reaction	of	2	
with	 the	appropriate	chloroacetone	or	‐bromoacetophenone,	
in	pyridine	to	give	a	product	identical	in	all	aspects	(m.p.,	mixed	
m.p.,	and	spectra)	with	4a	and	4b,	respectively	(Scheme	1).		

Condensation	 of	 compound	 1	 with	 ethyl	 acetoacetate	 in	
presence	 of	 ammonium	 acetate	 in	 acetic	 acid	 afforded	 the	
corresponding	 ethyl	 2‐methyl‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)‐4‐phenylpyridine‐3‐carboxylate	 (5)	 (Scheme	 2).	
Similarly,	the	reaction	of	compound	1	with	malononitrile,	ethyl	
cyanoacetate,	 cyanoacetamide,	 benzoylacetonitrile,	 2‐
cyanothioacetamide,	 3‐methyl‐1H‐pyrazol‐4‐one	 or	 1‐phenyl‐
3‐methyl‐1H‐pyrazol‐4‐one	yielded	the	corresponding	pyridine	
derivatives	 6‐10,	 3‐methyl‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)‐4‐phenyl‐1H‐pyrazolo[3,4‐b]pyridine	(11a)	and	3‐
methyl‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐1,4‐di‐
phenyl‐1H‐pyrazolo‐[3,4‐b]pyridine	 (11b)	 in	 good	 yields,	
respectively	 (Scheme	 2).	 The	 structures	 of	 the	 synthesized	
compounds	 were	 confirmed	 on	 the	 basis	 of	 their	 elemental	
analysis	and	alternative	synthetic	route.	Thus,	one	pot	reaction	
of	 1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)ethanone,	 benz‐
aldehyde,	 appropriate	 ethyl	 acetoacetate,	 malononitrile,	 ethyl	
cyanoacetate,	 cyanoacetamide,	 benzoylacetonitrile,	 cyano‐
thioacetamide,	 3‐methyl‐1H‐pyrazol‐4‐one	 or	 1‐phenyl‐3‐
methyl‐1H‐pyrazol‐4‐one	 and	 excess	 ammonium	 acetate	 in	 n‐
butanol	 gave	 identical	 product	 in	 all	 aspects	 (mp.,	mixed	mp.	
and	spectra)	with	corresponding	compounds	5‐11	(Scheme	2).	
2‐(5‐Methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐phenyl‐6‐	
substituted	pyridine	12a‐f	were	also	prepared	in	good	yield	by	
Krohnke	reaction	via	tratment	of	1	with	1‐(2‐oxo‐2‐substituted	
ethyl)‐pyridinium	bromides	in	glacial	acetic	acid.	

2‐Mercapto‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐
phenyl‐pyridine‐3‐carbonitrile	 (10)	 was	 reacted	 with	 each	 of	
ethyl	 chloroacetate,	 chloroacetone,	 ω‐bromoacetophenone,	
chloroacetonitrile	 or	 iodomethane	 gave	 corresponding	 S‐
alkylated	derivatives	13a‐f,	respectively.	Structures	13a‐f	were	
elucidated	 by	 elemental	 analysis,	 spectral	 data	 and	 chemical	
transformation.	Thus,	boiling	pyridine	derivatives	in	ethanol	in	
presence	 of	 catalytic	 amount	 of	 piperidine	 afforded	 2‐
substituted	 6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐
phenylthieno[2,3‐b]pyridin‐3‐amine	 derivatives	 14a‐c,	
respectively	(Scheme	3).	

Structures	14e	was	converted	to	2‐(5‐methyl‐1‐phenyl‐1H‐
[1,2,3]triazol‐4‐yl)‐4‐phenyl‐7H‐9‐thia‐1,5,7‐triaza‐fluoren‐8‐
one	 (15)	 and	 2‐(5‐methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐4‐
phenyl‐9‐thia‐1,5,7‐triaza‐fluoren‐8‐ylamine	(16)	by	its	boiling	
in	 formic	 acid	 and	 formamide,	 respectively.	 Also,	 compound	
14e	 reacted	 with	 triethyl	 orthoformate	 in	 acetic	 anhydride	



Abdelhamid	et	al.	/	European	Journal	of	Chemistry	3	(3)	(2012)	322‐331	 331	
 

gave	 ethyl	 N‐[2‐cyano‐6‐(5‐methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐
4‐yl)‐4‐phenyl‐thieno[2,3‐b]pyridin‐3‐yl]‐formimidate	 (17),	
which	was	converted	to	16	with	ammonia	(Scheme	3).		

Also,	compound	15	was	converted	to	8‐chloro‐2‐(5‐methyl‐
1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐4‐phenyl‐9‐thia‐1,5,7‐triaza‐
fluorene	 (18)	 by	 reaction	 with	 phosphrous	 oxychloride.	 The	
chloro	 derivative	 18	 was	 reacted	 with	 sodium	 azide	 and	
hydrazine	 hydrate	 gave	 8‐azido‐2‐(5‐methyl‐1‐phenyl‐1H‐
[1,2,3]triazol‐4‐yl)‐4‐phenyl‐9‐thia‐1,5,7‐triazafluorene	 (19)	
and	 [2‐(5‐methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐4‐phenyl‐9‐
thia‐1,5,7‐triaza‐fluoren‐8‐yl]‐hydrazine	 (20)	 in	 a	 good	 yield.	
The	 later	 was	 converted	 to	 8‐(5‐methyl‐1‐phenyl‐1H‐
[1,2,3]triazol‐4‐yl)‐6‐phenyl‐10‐thia‐1,2,3,3a,5,9‐hexaaza‐
cyclopenta[a]fluorene	 (21)	 by	 reaction	with	 nitrous	 acid	 at	 0	
oC.		

On	 the	 other	 hand,	 treatment	 of	 14a	 with	 hydrazine	
hydrate	 gave	 3‐amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐
4‐yl)‐4‐phenylthieno‐[2,3‐b]pyridine‐2‐carbohydrazide	 (22).	
Structure	of	22	was	confirmed	by	elemental	analysis,	 spectral	
data	 and	 chemical	 transformation.	Thus,	22	was	 reacted	with	
each	 of	 ethyl	 acetoacetate,	 acetylacetone	 or	 nitrous	 acid	
afforded	 2‐[3‐amino‐6‐(5‐methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐
yl)‐4‐phenylthieno[2,3‐b]pyridine‐2‐carbonyl]‐5‐methyl‐
2,4‐dihydro‐pyrazol‐3‐one	 (23a),	 [3‐amino‐6‐(5‐methyl‐1‐
phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐4‐phenyl‐thieno[2,3‐b]‐pyridin‐
2‐yl]‐(3,5‐dimethyl‐pyrazol‐1‐yl)‐methanone	 (23b)	 and	 (3‐
amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐4‐
phenylthieno[2,3‐b]‐pyridin‐2‐yl)azidomethanone	 (26),	
respectively	 (Scheme	 4).	 Structures	 23	 were	 elucidated	 by	
elemental	analysis,	spectral	data	and	chemical	 transformation.	
Thus,	 benzenediazonium	 chloride	 was	 reacted	 with	 23a	 and	
23b	in	ethanolic	sodium	acetate	solution	at	0	oC	afforded	2‐[3‐
amino‐6‐(5‐methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐4‐
phenylthieno[2,3‐b]pyridine‐2‐carbonyl]‐5‐methyl‐4‐(phenyl‐
hydrazono)‐2,4‐dihydro‐pyrazol‐3‐one	 (24a)	 and	 [3‐amino‐6‐
(5‐methyl‐1‐phenyl‐1H‐[1,2,3]triazol‐4‐yl)‐4‐phenyl‐
thieno[2,3‐b]pyridin‐2‐yl]‐(3,5‐dimethyl‐4‐phenylazoyrazol‐1‐
yl)‐methanone	 (24b),	 respect‐tively.	 Also,	 compounds	 24a,b	
were	obtained	by	reaction	of	22	with	 the	appropriate	of	ethyl	
2‐(2‐phenylhydrazono)‐3‐oxobutanoate	 (25a)	 and	 3‐(2‐
phenylhydrazono)pentane‐2,4‐dione	(25b),	respectively.	

Compound	26	was	reacted	with	the	appropriate	aniline,	4‐
toluidine,	 4‐anisidine,	 3‐amino‐5‐phenylpyrazole,	 anthranilc	
acid,	 phenol,	 4‐nitrophenol	 or	 picric	 acid	 afforded	 urea	
derivatives	 27a‐d,	 3‐(3‐amino‐6‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐
triazol‐4‐yl)‐4‐phenylthieno‐[2,3‐b]pyridin‐2‐yl)quinazoline‐
2,4(1H,3H)‐dione	(28)	and	aryl	3‐amino‐6‐(5‐methyl‐1‐phenyl‐
1H‐1,2,3‐triazol‐4‐yl)‐4‐phenylthieno‐[2,3‐b]pyridin‐2‐
ylcarbamate	29a‐c,	respectively.	

	
4.	Conclusion	
	

The	 present	 work	 describes	 the	 synthesis	 of	 5‐
arylazothiazole,	pyridine	and	thieno[2,3‐b]pyridine	derivatives	
contaninig	1,2,3‐triazole	moiety	in	a	good	yields	by	reaction	of	
1‐(5‐methyl‐1‐phenyl‐1H‐1,2,3‐triazol‐4‐yl)‐3‐phenylprop‐2‐
en‐1‐one	and	different	reagents.		 	
	
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