Synthesis, characterization, and dyeing performance of some azo thienopyridine and thienopyrimidine dyes based on wool and nylon

Article abstract of DOI:10.1002/jhet.3854

A string of novel heterocyclic mono azo dyes were synthesized and their utilization in dyeing different fabrics as wool and nylon were discussed. Thienopyridine azo dyes 4 and 6were prepared by reaction of chloro acetamidederivative 2 with diamino compounds to yield 3 and 5, followed by reaction with NaNO₂/HCl and coupling with nucleophilic reagent. One-pot reaction of chloro acetamide 2 with ammonium thiocyanat in solvent ethanol gave the unexpected thienopyrimidine derivative 7, which contain two active sites, the former is primary amine that was able to form diazonium salt that coupled with N,N-dimethylaniline, resorcinol, and/or self-coupling to afford the azo dyes 8-10, and the latter is active methylene group that underwent coupling with different diazonium salts to give the azo thienopyrimidine derivative dye 11-15. The dyeing performance of these azo dyes had been investigated in terms of their dyeing behavior and fastness properties on different fabrics. Results showed that the color strength (K/S) values, as well as, washing, rubbing, and resistance to acid, alkali and light showed high efficiency of these heterocyclic mono azo dyes to dye wool rather than nylon fibers.

Full text of DOI:10.1002/jhet.3854

Received: 30 September 2019
DOI: 10.1002/jhet.3854
Revised: 20 November 2019
Accepted: 25 November 2019
A R T I C L E
Synthesis, characterization, and dyeing performance
of some azo thienopyridine and thienopyrimidine
dyes based on wool and nylon
Mohsen K. A. Regal | El-Hady Rafat | Nour E. A. Abd El-Sattar
Chemistry Department, Faculty of
Abstract
Science, Ain Shams University, Abassia,
Cairo, Egypt
A string of novel heterocyclic mono azo dyes were synthesized and their
utilization in dyeing different fabrics as wool and nylon were discussed.
Thienopyridine azo dyes 4 and 6were prepared by reaction of chloro
acetamidederivative 2 with diamino compounds to yield 3 and 5, followed by
Correspondence
Nour E. A. Abd El-Sattar, Chemistry
Department, Faculty of Science, Ain
Shams University, Abassia, Cairo 11566,
Egypt.
reaction with NaNO /HCl and coupling with nucleophilic reagent. One-pot
2
reaction of chloro acetamide 2 with ammonium thiocyanat in solvent ethanol
gave the unexpected thienopyrimidine derivative 7, which contain two active
sites, the former is primary amine that was able to form diazonium salt that
coupled with N,N-dimethylaniline, resorcinol, and/or self-coupling to afford the
azo dyes 8-10, and the latter is active methylene group that underwent coupling
with different diazonium salts to give the azo thienopyrimidine derivative dye
Email: nourel-dinahmed@sci.asu.edu.eg
11-15. The dyeing performance of these azo dyes had been investigated in terms
of their dyeing behavior and fastness properties on different fabrics. Results
showed that the color strength (K/S) values, as well as, washing, rubbing, and
resistance to acid, alkali and light showed high efficiency of these heterocyclic
mono azo dyes to dye wool rather than nylon fibers.
1
| INTRODUCTION
it is used in many biomedical applications or conjugated
[
17]
with bioactive molecules. Wool fiber has high strength,
resiliency, and elasticity; moreover, wool has excellent dye
ability and comfortability, which gained an incomparable
Azo dyes containing thiophene nucleus generally show a
wide range of color, which has definite wavelength similar
to aniline-based azo dyes, and characterized by high
extinction coefficient.
eral environmental concerns owing to their wide spread,
which has been enhanced due to the textile industry revo-
lution of synthetic fibers such as polyester. Azo dyes
mostly have low solubility in water and to increase its sol-
ubility in water it should be minced to a very low particle
size using a surfactant (dispersing agent) or by using a car-
[
18–20]
interest in creating novel ideas for wool fibers.
[1–6]
Most of azo dyes have raised sev-
Nylon fiber has a number of notable characteristics
such as flexibility in surface functionalities and mechani-
cal presentation making it better to many applications
and other forms of natural polymeric and/or synthetic
[7]
[
21]
materials.
[8–14]
rier, which added during dyeing process.
2 | RESULTSAND DISCUSSION
Wool fiber is regarded as an abundant source for struc-
tural protein, which is related in general as wool keratin,
which are biocompatible and biodegradable. So that,
Accordingly, the present study was devoted to synthesis a
string of novel heterocyclic mono azo dyes and to
[15]
[16]
J Heterocycl Chem. 2019;1–10.
wileyonlinelibrary.com/journal/jhet
© 2019 John Wiley & Sons, Ltd.
1

2
REGAL ET AL.
investigate their dyeing performance on the fabrics as
wool and nylon. 2-Amino-3-cyano thiophene derivative
Treatment of acetamide derivative (2) with ammo-
nium thiocyanate in equivalent molar ratio in a mixture
of boiling dioxane/ethanol as solvent for 4 hours afforded
the unexpected product of ethyl 2-((4-amino-5, 6, 7,
8-tetrahydrobenzo [4,5]thieno[2,3-d] pyrimidin-2-yl)
thio)ethanoate (7).
[
22]
(
1) was prepared by Gewald reaction.
The free
amino group of 1 underwent nucleophilic displace-
ment when treated with chloroacetyl chloride to give
2
2
-chloro-N-(3-cyano-4,5,6,7-tetrahydrobenzo [b]thiophen-
-yl)ethanamide (2) (Scheme 1).
The formation of thienopyrimidine derivative 7 may
be explained by the proposed mechanism as shown in
Scheme 3. The thiocyanate anion underwent nucleophilic
displacement by chloride followed by cyclization to give
thiazole intermediate (not isolated) then imino group
attack on cyano to forming the unstable second interme-
diate thiazolopyrimidine (not isolated) and finally thia-
zole ring opening by ethanol to gives the more stable
ester 7. The ester of 7 was established by IR, which
showed a band at 1739 cm− attributed for C O of ester
Reaction of acetamide derivative 2 with 1,4-diamino ben-
/
zene and/or 4,4 −diamino biphenyl in dioxane under reflux
conditions afforded thiopheneacetamide derivative(3)
0
0
and 2-((4 -amino-[1,1 -biphenyl]-4-yl)amino)-N-(3-cyano-
,5,6,7-tetrahydrobenzo[b]thiophen-2-yl)acetamide (5),
respectively, (Scheme 2). The structure of compounds
and 5 was confirmed by the presence of three absorp-
4
3
tion signals at chemical shift 8.1, 8.6, and 11.9 ppm for
1
compound 3 and at 7.8, 7.9, and 11.9 ppm for compound
1
−1
5
in the HNMR spectra corresponding to three different pro-
group and two bands at 3500 and 3295 cm characteris-
1
tons of NH in addition to protons of aromatic absorption. In
tic for NH of NH . HNMR showed signals at chemical
2
continuation of this point, we dissolved compound 3 and/or
shift 1.17 (t), 4.13 (q) attributed to CH and CH of ester
3
2
5
in HCl then added sodium nitrite solution in order to form
beside peaks of cyclohexene and S-CH protons, also MS
2
the corresponding diazonium salt, which underwent cou-
pling and acid catalyst cyclization when treated with acti-
vated aromatic compounds like 2-naphthol in NaOH and/or
N,N-dimethylaniline in acetic acid to obtain orange crystals
of azo thienopyridone derivatives 4 and 6 (Scheme 2). The
structures of both azo thienopyridones 4 and 6 were
proved by disappear of CN band and appearance of enolic
hydroxyl and carbonyl bands in IR absorptions, as well
spectra have peak at m/z 323[M].
Compound 7 contain two active sites able to forming
new azo dye, the amino group and active methylene
group our work focus on coupling reactions on this two
active centers.
The free amino group on pyrimidine nucleus in
thienopyrimidine derivative 7 behaves the same character
as primary aromatic amine, which undergoes reaction with
sodium nitrite to forming a relatively stable corresponding
1
as HNMRsignals.
SCHEME 1 Synthesis of
thiophenyl amide 2
SCHEME 2 Formation of azo
thienopyridones 4 and 6

REGAL ET AL.
3
SCHEME 3 The suggested
mechanism for the formation of
thienopyrimidine derivative 7
SCHEME 4 Coupling of thienopyrimidine diazonium salt with different nucleophilic reagents
ꢀ
diazonium salt at temperature between 0 and 5 C. This dia-
zonium salt coupled with different activated nucleophilic
reagents such as N,N-dimethylaniline, resorcinol, and
ethyl 2-((4-amino-5,6,7,8-tetrahydrobenzo [4,5]thieno[2,3-d]
pyrimidin-2-yl)thio) ethanoate7, affording the azo coupling
products (8-10), respectively (Scheme 4). The products 8 and
aromatic amines such as p-amino benzene sulphonic
acid, p-toulidine, aniline, o-phenylendiamine and finally
α-naphthyl amine with HCl and sodium nitrite at 0-5 C
for 1 hour, afforded azo coupling products 11-15, respec-
tively (Scheme 5). All the products accompanied with
ꢀ
appearance of NH as present in compound 7 and exist in
2
9
1
accompanied with disappearance of NH , while compound
0 still appear in IR as well as HNMRand CNMR.
two tautomeric forms azo-form (A) and aryl hydrazones
form (B) (Figure 1), which was proved by IR showing
2
13
1
−
1
Thieno pyrimidine derivative 7 contains active methy-
two absorption bands for carbonyl at 1738 cm attrib-
−1
lene group at side chain adjacent to ester group has
nucleophalic character, capable to couple with different
diazonium salts, that formed from interaction of primary
uted to azo-form (A), at 1673 cm qualified for aryl
1
hydrazones conjugated ester (B), in addition to HNMR
13
and CNMR spectra.

4
REGAL ET AL.
SCHEME 5 Coupling of thienopyrimidine 7 with different aromatic diazonium salts
3
| EXPERIMENTAL
All melting points measured on an electric melting point
apparatus were uncorrected. The infrared spectra were
recorded using potassium bromide disks on a Pye Unicam
(A)
(B)
1
SP-3-300 infrared spectrophotometer. HNMR spectra were
FIGURE 1 The two tautomeric forms azo-form (A) and aryl
hydrazones form (B) of compound 7
run at 300 MHz, on a Varian Mercury VX-300 NMR spec-
trometer using TMS as an internal standard in deuterated
dimethyl sulphoxide (DMSO-d ). Chemical shifts δ are
quoted in ppm and CNMR spectra were recorded on the
same spectrophotometer at 75 MHz and referenced to sol-
filtered off, dried and crystallized from dioxane, afforded
6
13
compound 3 as pale yellow crystals, Yield: 3.19 g (98%); m.p:
ꢀ
132-134 C. IR (KBr) showed absorption bands at frequency
−
1
−1
−1
vent signal δ = 39.5 ppm for DMSO-d .The mass spectra
3275, 3225 cm
(NH), 3089 cm
(Ar H), 2945 cm
6
(Aliph. C H), 2199 cm− (CN), 1708 cm−1 (C O). H-NMR
1
1
were recorded on Shimadzu GCMS-QP-1000EX mass spec-
trometers at 70 eV. All the spectral measurements were car-
ried out at the NMR laboratory of Cairo University, Egypt,
the NMR laboratory of Faculty of Pharmacy; Ain shams
University, Egypt. The Micro analytical data were measured
in Central Lab of Cairo University, Egypt; and the Ministry
of Defense Chemical Laboratories, Egypt, and at the Micro
Analytical Center of Ain Shams University, Egypt. All the
chemical reactions were monitored by TLC.
(300 MHz, DMSO-d ):δ (ppm) 1.83 (t,4H, 2CH ), 2.68-2.71
6
2
(m, 2H, CH ), 2.89-2.92 (m, 2H, CH ), 4.31(s,2H, N CH ),
2
2
2
7.33 (d, j = 8 Hz, 2H, Ar-H), 7.52(d, j = 7.9 Hz, 2H, Ar-H), 8.1
(s, 1H, NH), D O exchangeable, 8.6 (s, 1H,NH), D O
2
2
exchangeable 11.9 (s,2H,NH2), D O exchangeable.MS
2
showed the parent peak at m/z (% abundance) 326 (8%).
Anal. Calculated forC H N OS (326.12): C, 62.55; H,
17 18 4
5.56; N, 17.16; Found: C, 62.81; H, 5.78; N, 17.29.
3
.1 | Synthesis of 2-(4-aminophenyl)
amino)-N-(3-cyano-4,5,6,7-tetrahydrobenzo
b]thiophen-2-yl)acetamide (3)
3.2 | Synthesis of 2-hydroxy-3-((4-((2-
hydroxynaphthalen-1-yl)diazenyl) phenyl)-
amino)-5,6,7,8-tetrahydrobenzo[4,5]thieno
[
[
2,3-b] pyridin −4(3H)-one (4)
Heating of chloroacetamide 2 (2.54 g, 0.01 mol) with
0.01 mol) of 1,4-diamino benzene in dioxane (50 mL) for
hours under reflux condition, the solid separated was
(
4
Solution of compound 3 (3.26 g, 0.01 mol) in dil HCl
(20 mL, 10%) was added to sodium nitrite solution

REGAL ET AL.
5
0
(
1
30 mL, 0.01 mol), the reaction mixture was stirred for
hour in ice bath to form the diazonium salt of com-
pound 3. A solution of 0.01 mol of 2-naphthol in NaOH
3.4 | Synthesis of 3-((4 -
((4-(dimethylamino)phenyl)diazenyl)-
[1,1 -biphenyl]-4-yl)amino)-2-hydroxy-
5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-b]
0
(
10 mL, 10%) was cooled and kept the temperature
ꢀ
between 0 and 5 C for 45 minute, the diazonium salt of
compound 3 was added drop wise in a period of half
hour, stirring well for 4 hours in ice bath, filtered off the
solid obtained, washed with water (100 mL) then
washed with diethyl ether (20 mL) crystallized from eth-
anol to obtain 4 as orange crystals. Yield: 3.37 g (74%);
m.p: 240-242 C. (UV-vis) λ maxwas 438 nm. IR spec-
trum (KBr) showed absorption bands at frequency at
3
C H), 1715 cm (C O) and absent of (CN) absorption
band. HNMR (300 MHz, DMSO-d ): δ(ppm) 1.82 (t,
4
CH ), 6.86 (d, j = 8 Hz, 2H, Ar-H), 7.31 (d, j = 8 Hz, 1H,
Ar-H), 7.42 (d, j = 8 Hz, 2H, Ar-H), 7.41-7.66 (m, 5H,
Ar-H), 7.8 (s, 1H, NH), D O exchangeable, 7.9 (s,
2
pyridin-4(3H)-one (6)
Dissolve (4.02 g, 0.01 mol) of acetamide derivative 5 in
dil. HCl (20 mL, 10%) then add (0.01 mol) of sodium
nitrite solution, stirring for 1 hour in ice bath to forming
the diazonium salt of compound 5, dissolve (0.01 mol) of
N,N-dimethyl aniline in 10 mL of acetic acid the solution
ꢀ
ꢀ
was cooled for 45 minute at 0-5 C, the diazonium salt of
449 cm− (OH), 3249 cm (NH), 2925 cm (Aliph.
1
−1
−1
compound 5 was added drop wise in a period of half
hour, stirring well for 4 hours in ice bath, the solid
obtained was filtered off, washed with water (100 mL)
then washed with diethyl ether (50 mL), crystallized from
dioxane to gives 6 as orange crystals. Yield: 4.16 g(78%);
m.p: 221-223 C. (UV -vis) λ max was 441 nm. IR (KBr)
showed absorption bands at frequency at 3441 cm (OH),
(NH), 2924 cm (Aliph. C H), 1744 cm
(C O), HNMR (300 MHz, DMSO-d ):δ(ppm) 1.7(t, 4H,
−
1
1
6
H, 2CH ), 2.74-2.81 (m, 2H, CH ,), 2.89-2.93 (m, 2H,
2 2
2
ꢀ
−
1
2
−
1
−1
−1
H,2OH), D O exchangeable, 10.1 (s, 1H, OH),D O
3180 cm
2
2
1
3
1
exchangeable. C NMR (75 MHz, DMSO-d ) δ (ppm):
6
6
1
1
1
60.2, 155.6, 150.3, 148.0, 146.3, 142.3, 137.6, 129.5,
28.5, 126.6, 125.3, 120.8, 118.5, 116.9, 112.6, 109.3,
05.6101.3, 99.3, 90.8, 25.4, 23.6, MS showed the parent
2CH ), 2.76-2.78 (m, 4H, 2CH ), 3.01 (s, 6H, 2CH ), 6.85
2
2
3
(d, j = 7.8 Hz, 2H, Ar-H), 7.31 (d, j = 6.8 Hz, 2H, Ar-H),
7.52 (d, j = 7.6 Hz, 2H, Ar-H), 7.63-7.81 (m,6H,Ar-H),8.1
(s, 1H, NH), D Oexchangeable, 9.6(s, 2H, 2OH), D O
peak at m/z (% abundance) 482 (2%). Anal. Calculated
for C H N O S (482.14): C, 67.20; H, 4.60; N, 11.61;
Found: C, 67.222; H, 4.65; N, 11.67.
2
2
exchangeable. MS showed the parent peak at m/z (%
abundance) 535 (8%). Anal. Calculated for C H N O S
2
7
22
4
3
31
29 5 2
(
5
534.22): C, 69.51; H, 5.46; N, 13.07; Found: C, 69.78; H,
.68; N, 13.21.
0
0
3
.3 | Synthesis of 2-((4 -amino-[1,1 -
biphenyl]-4-yl)amino)-N-(3-cyano-
,5,6,7-tetrahydro benzo[b]-thiophen-2-yl)
acetamide (5)
4
3.5 | Synthesis of ethyl 2-((4-amino-5,
6, 7, 8-tetrahydrobenzo [4,5] thieno[2,3-d]
pyrimidin-2-yl)thio) ethanoate (7)
/
Chloroacetamide 2 (2.54 g, 0.01 mol) and 4,4 −diamino
biphenyl (0.01 mol) in dioxane (30 mL) was heated
under reflux conditions for 4 hours, the solid formed
was filtered off, dried and crystallized from dioxane to
Refluxing 2-chloroacetamide 2 (2.54 g, 0.01 mol) with
ammonium thiocyanate (0.76 g, 0.01 mol) in a mixture of
1:1 dioxane-ethanol (100 mL) for 4 hours. The reaction
mixture was poured in ice water (200 mL), the precipitate
formed was filtered off, dried and crystallized from buta-
nol, afforded ethanoate 7 as pale yellow crystals. Yield:
gives compound 5, as green crystals, Yield: 3.89 g
ꢀ
(
97%); m.p:128-130 C. IR (KBr): showed absorption
−
1
bands at frequency at 3416, 3345, 3226 cm (NH),
928 cm (Aliph. C H), 2217 cm (CN), 1685 cm
C O). HNMR (300 MHz, DMSO-d ): δ(ppm) 1.9 (t,
−
1
−1
−1
ꢀ
2
(
3.1 g (96%); m.p: 123-125 C. IR (KBr) showed absorption
1
−1
bands at frequency 3296, 3134 cm characteristic for pri-
6
−
1
4
H, 2CH ), 2.72-2.76 (m, 2H, CH ), 2.90-2.94 (m, 2H,
mary amino group (NH ), 1739 cm (C O ester), as well
2
2
2
1
CH ), 4.2 (s,2H, N CH ) 6.9 (d, j = 8.1 Hz, 2H, Ar-H),
as disappearance the absorption band for CN, HNMR
2
2
7
7
.4 (d, j = 8 Hz, 2H, Ar-H), 7.51-7.74 (m, 4H, Ar-H),
(300 MHz, DMSO-d ):δ(ppm) 1.17 (t.3H, CH ), 1.79-1.81
6
3
.81(s, 1H, NH), D O exchangeable, 7.9(s, 1H, NH),
(m,4H, 2CH ), 2.70-2.72 (m, 4H, 2CH ), 3.9 (s.2H, SCH ),
2
2 2 2
D O exchangeable, 11.9 (s, 2H, NH ), D O exchange-
4.13 (q, j = 6.1 Hz, 2H, OCH ), 6.9 (s, 2H, NH ) D O
2 2 2
2
2
2
able. MS showed the parent peak at m/z (% abun-
dance) 402 (4%). Anal calculated for C H N OS
exchangeable, MS showed the parent peak at m/z (%
abundance): 323 (35%). Anal. Calculated for C H N O S
2
3
22
4
14 17 3 2 2
(
6
402.15): C, 68.63; H, 5.51; N, 13.92; Found: C,
8.75; H, 5.62; N, 14.05.
(323.43): C, 51.99; H, 5.30; N, 12.99 Found: C, 52.11; H,
5.21; N, 13.11.

6
REGAL ET AL.
3
.6 | General procedure for azo coupling;
2.87-2.89 (m, 2H, CH ), 3.7 (s.2H, S CH ), 4.1 (q,
2
2
preparation of diazonium salt of compound
: Synthesis of compounds 8-10
j = 6.8 Hz, 2H, OCH ), 6.91 (s, 1H, Ar-H), 7.18 (d, 1H,
2
7
j = 7.6 Hz, Ar-H) 7.30 (d, 1H, j = 7.6 Hz, Ar-H), 12.6 (s,
2
H, 2OH) D O exchangeable. Anal. Calculated for
2
Dissolve 3.23 g (0.01 mol) of compound 7 in 20 mL of
HCl (10%) then add (0.01 mol) of sodium nitrite solu-
tion, stirring well for 1 hour, the solution was cooled at
C H N O S (444.53): C, 54.04; H, 4.53; N, 12.60;
20 20 4 4 2
Found: C, 54.06; H, 4.55; N, 12.63.
ꢀ
temperature between 0 and 5 C, the diazonium salt was
formed is added drop wise in a period of half hour to a
solution of different nucleophilic reagent such as N,N-
dimethyl analine (0.01 mol) in 10 mL of acetic acid, res-
orcinol (0.01 mol) in 10 mL of NaOH (10%), and/or
active methylene compound as ethyl 2-((4-amino-5,-
3.9 | Ethyl 2-((4-amino-5,6,7,8-
tetrahydrobenzo[4,5]thieno[2,3-d]
pyrimidin-2-yl)thio)-2-((2-((2-ethoxy-
2-oxoethyl)thio)-5,6,7,8-tetrahydrobenzo
[4,5]thieno[2,3-d]pyrimidin-4-yl)diazenyl)
acetate (10)
6
,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidin-2-yl)
thio) acetate (7) (0.01 mol) in acetic acid (10 mL), the
precipitated was formed, filtered off, washed with water
Crystallized from ethanol as yellow crystal. Yield: 5.32 g
(81%); m.p: above 300 C.(UV -vis) λ max was 453 nm. IR
ꢀ
(
100 mL) then washed with diethyl ether (50 mL ×2
times), which affording the azo dyes compounds 8-10,
respectively.
(KBr) showed absorption bands at frequency: 3299,
−1
−1
−1
3160 cm (NH ), 2933 cm (Aliph. C H), 1737, 1669 cm
2
(
(
C O of two ester), 1547.36 cm− (N N). HNMR
1
1
300 MHz, DMSO-d ):δ(ppm):1.21 (t, 3H, CH ), 1.28 (t,
6
3
3
.7 | Ethyl 2-((4-((4-(dimethylamino)
phenyl)diazenyl)-5,6,7,8-tetrahydrobenzo
4,5]thieno [2,3-d]pyrimidin-2-yl)thio)
3H, CH ), 1.81-1.83 (m,8H, 4CH ), 2.68-2.71 (m, 8H,
3
2
4CH ), 3.72 (s.1H, S CH), 3.83 (s,2H, S CH ), 4.12(q,
2
2
[
j = 6.9 Hz, 2H, OCH ), 4.23(q, j = 6.9 Hz, 2H, OCH ), 7.0
2 2
1
3
acetate (8)
(s, 2H,NH ) D O exchangeable. C NMR (75 MHz,
2 2
DMSO-d ) δ (ppm): 180.5, 176.2, 174.6, 174.5, 170.3,
6
Crystallized from ethanol as yellowish green crystals.
Yield: 2.55 g(56%); m.p: 186-188 C.(UV -vis) λ max was
162.3, 160.5, 156.3, 140.3, 130.9, 122.3, 115.8, 78.6, 62.3,
42.5, 28.6, 24.6, 22.8, 21.7, 20.8, 18.6, 15.4. Anal. Calcu-
lated for C H N O S (657.85): C, 51.12; H, 4.75; N,
ꢀ
3
97 nm. IR(KBr) no absorption band for NH but showed
2
8
31
7
4 4
−
1
absorption bands at frequency 3063 cm (Ar C H),
2
14.90; Found: C, 51.24; H, 4.88; N, 15.11.
−
1
−1
−1
936 cm (Aliph C H), 1669 cm (C O), 1615 cm
−
1
1
(
C N), 1540 cm (N N). HNMR (300 MHz, DMSO-
d ): δ(ppm) 1.2 (t.3H, CH ), 1.69-1.71(m, 4H, 2CH ),
3.10 | General procedure for azo
coupling of compound 7 with different
diazonium salts: Synthesis of
compounds 11-15
6
3
2
2
.70-2.72 (m,2H,CH ), 2.80-2.82 (m, 2H,CH ), 2.9 (s, 6H,
2 2
N[CH ] ), 3.7 (s.2H, SCH ),4.2 (q, j = 6.8 Hz,2H, CH ),
3
2
2
2
7
.61 (d, 2H, j = 7.6 Hz ,Ar-H), 7.81(d, 2H, j = 7.6 Hz,
Ar-H). Anal. Calculated for C H N O S (455.60): C,
2
2
25
5
2 2
5
5
8.00; H, 5.53; N, 15.37 Found: C, 58.15; H,
.68; N, 15.49.
A solution of (0.01 mol) primary aromatic amines,
namely p-amino benzene sulphonic acid, p-toluidine,
aniline, o-phenylene diamine, and/or 1-naphthyl
amine in 20 mL of HCl (10%) was added to
(0.015 mol) of sodium nitrite solution, the reaction
mixture was stirred well in ice bath at temperature
3
.8 | Ethyl 2-((4-((2,4-dihydroxyphenyl)
diazenyl)-5,6,7,8-tetrahydrobenzo [4,5]
ꢀ
thieno[2,3-d]pyrimidin-2-yl)thio)acetate (9)
between 0 and 5 C for 1 hour until the diazonium
salt is formed, then added a solution of acetate deriv-
ative 7 (3.23 g, 0.01 mol) in 10 mL of acetic acid;
dropwise in a period of 30 minutes; the reaction was
Crystallized from methanol as yellowish brown crystals,
Yield: 3.32 g(75%); m.p:184-186 C. (UV -vis) λ max was
ꢀ
ꢀ
4
3
88 nm IR (KBr) showed absorption bands at frequency
done in ice bath 0-5 C with stirring for 4 hours, the
497 cm− (OH),3050 cm (Ar C H), 2934 cm (Aliph
1
−1
−1
formed precipitated was filtered off, dried and
washed by 100 mL of water, then washed by diethyl
ether (50 mL × 2 times) afforded the azo coupling
compounds 11-15, respectively.
−
1
−1
−1
C H), 1735 cm (C O), 1652 cm (C N), 1567 cm
1
(
N N). HNMR (300 MHz, DMSO-d ):δ(ppm) 1.2 (t.3H,
6
CH ), 1.79-1.81 (m,4H, 2CH ), 2.66-2.68 (m, 2H, CH ),
3
2
2

REGAL ET AL.
7
−
1
−1
−1
−1
3
.11 | 4-((1-((4-Amino-5,6,7,8-
3124.8 cm (NH ), 3064.98 cm (Ar. C H), 2976.9 cm
2
−
1
tetrahydrobenzo[4,5]thieno[2,3-d]
pyrimidin-2-yl)thio)-2-ethoxy-2-oxoethyl)
diazenyl)benzenesulfonic acid (11)
(Aliph, C H), 1736.2, 1662.6 cm (C O).1555.3 cm
(N N). H-NMR (300 MHz, DMSO-d ): δ(ppm) 1.29
1
6
(t,3H, CH ), 1.79-1.81 (m.4H, 2CH ), 2.88-2.91 (m,4H,
3
2
2
CH ) 3.6 (s, 1H, SCH), 4.1 (q, j = 6.9 Hz,2H, OCH ),
2
2
Crystallized from ethanol as orange crystal. Yield: 3.7 g
5.51 (broads, 2H,NH ) D O exchangeable, 7.22-7.43 (m,
2 2
ꢀ
(73%); m.p:183-185 C. (UV-vis) λ max was 442 nm. IR
5H, Ar-H), MS showed the parent peak at m/z (% abun-
dance):: 427 (12%). Anal. Calculated for C H N O S
21 5 2 2
(
3
(
(
KBr) showed absorption bands at frequency 3297,
20
122 cm− (NH ), 3064 cm
1
−1
(Ar, C H), 2932 cm
−1
−1
(427.11): C, 56.19; H, 4.95; N, 16.38; Found: C, 56.32; H,
5.23; N, 16.43.
2
−
1
Aliph. C H), 1737, 1669 cm
(C O), 1551 cm
1
N N). H-NMR (300 MHz, DMSO-d ): δ(ppm) 1.22
6
(
t,3H, CH ),1.78-1.81 (m.4H, 2CH ), 2.89 (m,4H, 2CH )
3
2
2
3
.58 (s, 1H, SCH), 4.21 (q, j = 6.8 Hz, 2H, OCH ), 7.01
3.14 | Ethyl −2-((4-amino-5,6,7,8-
tetrahydrobenzo[4,5]thieno[2,3-d]
pyrimidin-2-yl)thio)-2-((2-aminophenyl)
diazenyl)acetate (14)
2
(broads, 2H,NH ) D O exchangeable, 7.80 (d, j = 9 Hz,
2 2
2
1
H, Ar-H), 7.83(d, j = 9.1 Hz, 2H, Ar-H), 8.35 (broads,
H,SO H) D O exchangeable, MS showed the parent
3
2
peak at m/z (% abundance):: 507 (9.3%). Anal. Calculated
for C H N O S (507.07): C, 47.32; H, 4.17; N, 13.80;
Found: C, 47.63; H, 4.36; N, 13.46.
Crystallized from acetic acid as pale yellow crystal. Yield:
3.8 g(86%); m.p: 242-244 C. (UV-vis) λ max was 404 nm.
20
21 5 5 3
ꢀ
IR (KBr) showed absorption bands at frequency 3513,
−
1
−1
3
451, 3212, 3190 cm
(2NH ), 3064 cm
(Ar.C H),
2
−
1
−1
3
.12 | Ethyl −2-((4-amino-5,6,7,8-
2976 cm
(Aliph. C H), 1738, 1674 cm
(C O),
1
1
tetrahydrobenzo[4,5]thieno[2,3-d]
pyrimidin-2-yl)thio)-2-(p-tolyldiazenyl)
acetate (12)
1556 cm− (N N), H-NMR (300 MHz, DMSO-d6):
δ(ppm) 1.25 (t,3H, CH ), 1.85-1.87 (m.4H, 2CH ),
3
2
2.89-2.91 (m,4H, 2CH ) 3.6 (s, 1H, SCH), 4.1 (q, j = 6.8 Hz,
2
2
H, OCH ), 5.21 (broads, 2H,NH ) D O exchangeable,
2 2 2
Crystallized from dioxane as pale yellow. Yield: 3.88 g
6.78-7.12 (m, 4H, Ar-H), 7.42(broads, 2H,NH ) D O
2 2
ꢀ
13
(88%); m.p: 190-192 C. (UV-vis) λ max was 409 nm. IR
exchangeable, C NMR (75 MHz, DMSO-d ) δ (ppm):
6
(
KBr) showed absorption bands at frequency 3509,
175.2, 171.2, 159.3, 155.6, 144.3, 138.6, 134.3, 128.9, 126.3,
122.8, 120.8, 115.6, 112.7, 77.5, 64.3, 24.9, 22.2, 20.3, 14.9.
MS showed the parent peak at m/z (% abundance):
442 (11%). Anal. Calculated for C H N O S
20 22 6 2 2
−
1
−1
−1
3
2
1
449 cm (NH ), 3124 cm (NH), 3064 cm (Ar. C H),
2
975 cm− (Aliph C H), 1738, 1662 cm
1
−1
(C O),
556 cm− (N N). HNMR1 (300 MHz, DMSO-d ):δ
1
1
6
(
ppm):1.21 (t.3H, CH ), 1.85 (m,4H, 2CH ), 2.1 (s,3H,
(442.12): C, 54.28; H, 5.01; N, 18.99; Found: C, 54.32; H,
5.33; N, 18.43.
3
2
CH ), 2.69-2.71 (m, 2H, CH ), 2.82-2.84 (m, 2H, CH ),
3
2
2
3
.74 (s.1H, S CH), 4.12 (q, j = 6.9 Hz, 2H, OCH ), 5.51
2
(
2
broads, 2H,NH ) D O exchangeable, 7.45 (d, j = 8.4 Hz,
H, Ar-H), 7.62 (d, j = 8.4 Hz, 2H, Ar-H). C NMR
2 2
13
3.15 | Ethyl −2-((4-amino-5,6,7,8-
tetrahydrobenzo[4,5]thieno[2,3-d]
pyrimidin-2-yl)thio)-2-(naphthalen-
1-yldiazenyl)acetate (15)
(
1
2
75 MHz, DMSO-d6) δ (ppm): 174.2, 170.5, 160.5, 155.4,
48.2, 142.3, 137.9, 130.1, 128.3, 123.5, 115.6, 76.3, 62.3,
5.3, 23.6, 19.5, 14.9. MS showed the parent peak at m/z
(%
abundance):: 441 (7%). Anal. Calculated for
C H N O S (441.13): C, 57.12; H, 5.25; N, 15.86;
Found: C, 57.25; H, 5.17; N, 16.12.
Crystallized from ethanol as brownish orange. Yield:
4.14 g (87%); m.p:174-176 C. (UV-vis) λ max was 469 nm.
21
23 5 2 2
ꢀ
IR (KBr) showed absorption bands at frequency 3299,
−
1
−1
−1
−1
3
156 cm (NH ), 3055 cm
(Ar. C H), 2978 cm
2
−1
3
.13 | Ethyl −2-((4-amino-5,6,7,8-
(Aliph. C H), 1735, 1665 cm
(C O), 1547 cm
1
tetrahydrobenzo[4,5]thieno[2,3-d]
pyrimidin-2-yl)thio)-2-(phenyldiazenyl)
acetate (13)
(N N). HNMR (300 MHz, DMSO-d ):δ (ppm) 1.31(t,
6
3H, CH ), 1.79-1.81 (m.4H, 2CH ), 2.81-2.83 (m, 4H,
3
2
2CH ), 3.6(s, H, SCH), 4.1 (q, j = 6.4 Hz, 2H, OCH ),
2
2
7
.12-8.21 (m, 7H Aromatic) 10.11(s, 2H, NH ). MS
2
Crystallized from ethanol as pale yellow. Yield: 3.58 g
showed the parent peak at m/z (% abundance):: 477 (6%).
Anal. Calculated for C H N O S (477.13): C, 60.36; H,
4.85; N, 14.66; Found: C, 60.28; H, 5.15; N, 14.31.
ꢀ
(
(
84%); m.p: 173-175 C. (UV-vis) λ max was 431 nm IR
KBr) showed absorption bands at frequency 3297.9,
24
23 5 2 2

8
REGAL ET AL.
3.16 | Fabrics
TABLE 1 The color strength (K/S) values and colorimetric
data of nylon and wool fabrics dyed with synthesized dyes
Wool fabric was supplied from Misr for Spinning and
Weaving Company (Mahalla El-Kobra, Egypt) weight
Nu
Fabric
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
L*
a*
b*
K/S
1.61
1.45
2
Blank
92.48
83.57
89.66
82.91
69.73
50.30
74.3
2.12
0.16
3.31
0.35
6.53
−2.94
3.34
−0.29
7.7
−8.91
14.47
−4.6
17.12
9.07
−
2
2
05 g , 72 ends per inch, 64 picks per inch. Polyamide
2
fabric (100% nylon 66) of 110 g/m supplied by private
sector Co was scoured. Before using, the fabric was
treated with nonionic detergent at 50 C, washed several
4
ꢀ
1.77
2.61
4.99
2.17
1.94
2.59
1.74
2.28
5.47
2.86
1.64
2.74
1.86
2.6
time with water, bleached and dried thoroughly.
6
0.76
8
−3.97
19.65
10.34
13.9
3.17 | Dyeing of nylon and wool
80.38
75.36
82.32
85.9
procedures
9
Dyeing of wool and nylon fibers was performed by using
concentrations of 2% o.w.f (on the weight of fabric). The
wool and/or nylon was added to dying bath containing dyes
components that dissolve in water at PH = 5 (accustomed
−0.02
3.4
10
0.67
61.98
75.28
80.92
84.6
3.29
6.28
1.01
3.96
1.03
2.62
0.97
4.98
1.35
14.3
−4.32
23.39
7.98
1
1
1
2
ꢀ
by dil. acetic acid) at temperature 40 C. The temperature
11.26
4.83
ꢀ
ꢀ
ꢀ
was raised to 100 C with a rate 2 C/min and kept at 100 C
for 60 minutes. The fibers were next cooled and rinsed in a
80.20
86.19
82.07
84.16
80.98
67.9
16.97
0.31
raw tap water, and then washed in a bath of L.R. 50:1 using
ꢀ
2
g/L of nonionic detergent at 50 C for 30 minutes. Finally,
13
the dyed samples were dried at ambient temperature.
15.64
9.05
1.66
2.57
1.75
2.66
2.81
1
1
4
5
15.34
19.5
3.18 | Color measurements and color
fastness
68.02
8.86
Color of the dyed nylon and wool fabrics is a key impor-
tance due to the effect of the colored fabrics on the pro-
2
2
K=S = ð1−RÞ =2R−ð1−R Þ =2R
ð1Þ
o
o
[23]
duction demands and customer consumption.
In the
current work, of nylon and wool fabrics were our main
objective. To examine the color properties of the dyed
fabrics, the colorimetric data were measured for the dyed
nylon and wool fabrics using synthesized dyes.
where R is the decimal fraction of the reflectance of the
dyed fabric, R is the decimal fraction of the reflectance
o
of the undyed fabric, K is the absorption coefficient, and
S is the scattering coefficient.
Table 1 shows that all the dyed nylon and wool fab-
rics using synthesized dyes showed relatively moderate to
very good color strength (K/S) values, in compared with
blank selective Society2-(2-(3-Methyl-5-oxo-1-phenyl-1H-
pyrazol-4[5H]ylidene)hydrazinyl)-4,5,6,7-tetrahydro benzo[b]
3.20 | CIE lab difference
[24]
thiophene-3-carbonitrile,
the dyed nylon and wool fab-
Color measurements of treated textile, were made
according to the CIE (L*, a*, b*) system to evaluate the
color coordinates. In this system, L* refers to lightness/
darkness values from 100 to 0 representing white to black,
a* values run from negative (green) to positive (red), and
b* values run from negative (blue) to positive (yellow).
rics shows brilliant good to very good K/S values ranging
between 2 and 2.86 for the dyed nylon fabric and 1.64-5.47
for the dyed wool fabric using synthesized dyes.
3.19 | Color measurements
The colorimetric measurement of the dyed samples was mea-
sured using a Hunter Lab ultra Scan PRO spectrophotome-
ter. The analogous color strength value (K/S) was assessed by
3.21 | Fastness properties
Fastness properties were measured according to ISO
105-X12(1987), ISO 105-CO4 (1989), ISO105-EO4 (1989),
[6]
applying the KubelkaMunk equation (1) as follows:

REGAL ET AL.
9
TABLE 2 Fastness properties of nylon and wool fabrics dyed with synthesized dyes
Perspiration
Washing
Rubbing
Acidic
Alkaline
Nu
4
Fabric
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
Nylon
Wool
St.*
4
St.**
Alt.
4
Dry
4
Wet
4
St.*
4
St.* *
4
Alt.
4
St.*
4
St.**
4
Alt.
4
Light
3-4
3-4
2
4
4
4
4
4
4
4
4
4
4
4
4
6
8
9
3
3
2-3
2-3
2-3
4
2-3
2-3
2-3
4
2
3
3
2-3
2
3
3
2-3
2
2-3
3
2-3
3
2
2-3
3
2-3
3
2-3
3
2-3
3
2
2
2-3
4
2-3
4
2
4
4
4
4
4
4
4
4
3
3
2-3
4
2-3
4
2
3
3
2-3
4
3
3
2-3
4
2
4
4
4
4
4
4
4
4
1
1
1
1
1
1
0
1
2
3
4
5
3-4
2-3
2-3
3-4
3
3-4
2-3
2-3
3-4
3
3
3-4
2-3
2-3
3-4
3
3
3-4
2-3
2-3
3-4
3-4
4
3-4
2-3
2-3
3-4
3-4
4
3
3-4
2-3
2-3
3-4
3-4
4
3-4
2-3
2-3
3-4
3-4
4
3
3-4
2
2-3
2-3
3
2
2
2
2
2
2
2
3
3
3
3-4
2-3
3-4
2-3
3-4
2-3
3-4
2
3-4
4
2-3
4
3
3
4
4
4
4
4
3
3
3-4
4
3
2-3
4
3-4
4
3-4
4
3
3-4
4
3-4
4
3
4
4
4
4
4
3
3
3-4
3
3
2-3
3
3-4
3-4
3
3-4
3-4
3
3
3-4
3-4
3
3-4
3-4
3
3
3-4
3
3-4
3
3-4
2-3
2-3
3
3
2-3
2-3
2
2-3
2
2-3
2
2-3
2-3
2
2-3
2-3
2-3
2-3
2
Abbreviations: Alt., alteration in color; St.*, staining on cotton; St.**, staining on wool.
ISO 105-BO2 (1988) corresponding to color fastness to
rubbing, washing, acid and alkali perspiration, respec-
tively. For the fastness assessment, a rating scale of
and resistance to acid, alkali and light showed high effi-
ciency of these heterocyclic mon azo dyes to dyeing wool
rather than nylon fibers.
1
(poor) to 5 (excellent) was used.
It can be seen from Table 2 that all the dyed nylon and
REFERENCES AND NOTES
wool fabrics using synthesized dyes showed relatively poor
to very good fastness properties to washing, rubbing, acid
and alkali perspiration, ranging between 2 and 4 relative
to the blank selective thiophene azodye. On the other
hand, light fastness tests were carried out for 4 hours irra-
diation to the dyed samples using a XENOTEST 1200
apparatus at a relative air humidity of 65% and 50 C with
duration 4 hours. The prepared synthesized dyes show
poor to good as 1-2 to 3-4 and 4 light fastness.
[1] M. A. Gouda, M. A. Berghot, H. FakhrEldien, M. M. Girges,
J. Saudi Chem. Soc. 2016, 20, 151–7.
2] M. Metwally, A. Ebrahim, M. Amira, A. A. Fathy, Dyes Pig-
ments. 2012, 92(3), 902–8.
3] M. A. Metwally, E. Abdel-latif, A. M. Khalil, F. A. Amer,
G. Kaupp, Dyes Pigments 2004, 62(2), 181–95.
[
[
[
[
[
[
4] M. M. Kamel, R. M. El-Shishtawy, B. M. Youssef, H. Mashaly,
ꢀ
Dyes Pigments 2005, 65, 103–10.
5] M. M. Kamel, R. M. El-Shishtawy, B. M. Youssef, H. Mashaly,
Dyes Pigments 2007, 73(3), 279–84.
6] M. A. Hamed, K. Shaban, H. Kafafy, E. Gokha, I. El Sayed,
Egypt. J. Chem 2017, 2017, 89–95.
7] E. R. Reigel, J. A. Kent, Riegel's Handbook of Industrial
Chemsitry, 10th ed., Springer Pub, New York, NY 2003,
pp. 896–904.
4
| CONCLUSIONS
The present work demonstrates the synthesis of 10 novel
azo thienopyridine and thieno pyrimidine dyes and test-
ing their dying abilities on wool and nylon fabrics. The
color strength (K/S) values, as well as washing, rubbing,
[
8] A. D. Broadbent, Basic Principles of Textile Coloration, Society
of Dyers and Colorists, Thanet Press Ltd, Kent, West Yorkshire,
England 2001, pp. 322–31.
[9] C. C. Lai, K. M. Chen, Text. Res. J. 2008, 78, 382–9.

10
REGAL ET AL.
[
10] Z. Ren, C. Qin, R. C. Tanga, G. Chen, J. Soc. Dyers Color. 2012,
28, 147–52.
11] H. A. Eren, Color. Technol. 2007, 123(4), 224e9.
[21] H. R. Pant, H. J. Kim, L. R. Bhatt, M. K. Joshi, E. K. Kim,
J. I. Kim, A. Abdal-hay, K. S. Hui, C. S. Kim, Appl. Surf. Sci.
Part B 2013, 285, 538–44.
1
[
[
12] J. J. Lee, W. J. Lee, J. H. Choi, J. P. Kim, Dyes Pigments 2005,
[22] M. K. A. Regal, S. S. Shaban, S. A. El-Metally, J. Heterocycl.
6
5(1), 75–81.
13] S. M. Burkinshaw, B.-C. Koo, J. Korean Soc. Dyers Finishers
996, 8, 361–5.
14] J. Koh, A. J. Greaves, J. P. Kim, Dyes Pigments 2004, 60(2),
55–65.
Chem 2019, 56, 226–33.
[23] A. Al-Etaibi, M. A. El-Apasery, M. M. Kamel, Int. J. Curr.
Microbiol. Appl. Sci. 2015, 4, 923.
[24] M. A. Gouda, H. Fakhr Eldien, M. M. Girges, M. A. Berghot,
J. Saudi Chem. Soc. 2016, 20, 151–7.
[
[
[
1
1
15] A. Tachibana, Y. Furuta, H. Takeshima, T. Tanabe,
K. Yamauchi, J. Biotechnol. 2002, 93, 165–70.
[
[
16] J. G. Rouse, M. E. Van Dyke, Materials 2010, 3, 999–1014.
17] A. Kurimoto, T. Tanabe, A. Tachibana, K. Yamauchi, J. Biosci.
Bioeng. 2003, 96, 307–9.
How to cite this article: Regal MKA, Rafat E-H,
El-Sattar Nour E. A. Abd. Synthesis,
characterization, and dyeing performance of some
azo thienopyridine and thienopyrimidine dyes
based on wool and nylon. J Heterocycl Chem. 2019;
[
18] W. Xu, G. Ke, J. Wu, X. Wang, J. Eur. Polym. 2006, 42,
2
168–73.
[
19] S. S. Sun, R. C. Tang, Ind. Eng. Chem. Res. 2011, 50, 4217–24.
20] M. M. Hassan, J. F. Davies-McConchie, Ind. Eng. Chem. Res.
[
1–10. https://doi.org/10.1002/jhet.3854
2
012, 51, 9634–41.