Efficient Synthesis of Some New Chromenopyrimidine Azo- Dyes Catalyzed by Cu/SBA-15

Full text of DOI:10.1080/00304948.2018.1462066

Organic Preparations and Procedures International
The New Journal for Organic Synthesis
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Efficient Synthesis of Some New
Chromenopyrimidine Azo- Dyes Catalyzed by Cu/
SBA-15
Afsaneh Zonouzi, Hanieh Amini Shahrezaee, Alireza Rahmani, Forouzan
Zonouzi, Khosrou Abdi, Farzaneh T. Fadaei & Kurt Schenk
To cite this article: Afsaneh Zonouzi, Hanieh Amini Shahrezaee, Alireza Rahmani, Forouzan
Zonouzi, Khosrou Abdi, Farzaneh T. Fadaei & Kurt Schenk (2018) Efficient Synthesis of Some New
Chromenopyrimidine Azo- Dyes Catalyzed by Cu/SBA-15, Organic Preparations and Procedures
International, 50:3, 343-358, DOI: 10.1080/00304948.2018.1462066
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Organic Preparations and Procedures International, 50:343–358, 2018
Copyright Ó Taylor & Francis Group, LLC
ISSN: 0030-4948 print / 1945-5453 online
DOI: 10.1080/00304948.2018.1462066
Efficient Synthesis of Some New
Chromenopyrimidine Azo- Dyes Catalyzed
by Cu/SBA-15
Afsaneh Zonouzi,1,2 Hanieh Amini Shahrezaee,1 Alireza Rahmani,1
Forouzan Zonouzi,1,2 Khosrou Abdi,3 Farzaneh T. Fadaei,4
and Kurt Schenk5
1School of Chemistry, College of Science, University of Tehran, 14155–6455,
Tehran, Iran
2Pharmaceutical and Cosmetic Research Center (PCRC), University of Tehran,
Tehran, Iran
3Department of Medicinal Chemistry and Radio Pharmacy, Faculty of
Pharmacy, Tehran University of Medical Sciences, Tehran, Iran
4
ꢀ
Institute of Chemical Sciences and Engineering, Ecole
ꢀ ꢀ
Polytechnique Federale de Lausanne, CH-1015, Lausanne Switzerland
5
Institute of Physics, Ecole Polytechnique Federale de Lausanne, CH-1015,
Lausanne, Switzerland
ꢀ
ꢀ ꢀ
Azo compounds are among the largest and oldest classes of synthetic dyes produced on an
industrial scale1 with such applications as textile fiber dyeing,2 inkjet printing 1,3 sensors
2,4 liquid crystalline displays (LEDs),5 data storage,6 electro-optics,7 dye-sensitized solar
cells8 and biological applications including antimicrobial 39 and antifungal agents; and
they have proved to have anti-HIV activity.10 Azo-dyes have shown unique photochemi-
cal and photophysical properties. Azo chromophores undergo reversible light-driven cis-
trans isomerization around the azo bond11 which in turn causes concomitant changes in
structure, dipole moment and optical properties. Some azo dyes have been known to be
toxic,12 while others are even permitted to be used in pharmaceutical,13 cosmetic and per-
sonal care products.14
Received July 31, 2017; in final form December 15, 2017.
Address correspondence to Afsaneh Zonouzi, School of Chemistry, College of Science, Uni-
versity of Tehran, Tehran, 14155–6455, Iran. E-mail: zonouzi@khayam.ut.ac.ir
Color versions of one or more figures in this article can be found online at
www.tandfonline.com/uopp.
343

344
Zonouzi et al.
Chromenopyrimidine derivatives show a variety of interesting properties, among
which antitumor,15 analgesic,16 antimicrobial17 and anti-tubercular18 activities are the
most interesting. We have already reported the synthesis of some chromeno[2,3-d] pyrim-
idine derivatives;19,20 and, in continuation of our studies, we conducted a set of experi-
ments on the synthesis of chromeno[2,3-d]pyrimidines containing an azo-moiety using
copper based nano-catalysts.
SBA-15 type mesoporous silica21 has been long known as an excellent catalyst sup-
port.22,23 Direct and post-synthetic approaches have been used to load the pore channels
of this material with different catalysts.24 Many of the catalysts prepared through post-
synthetic grafting suffer from leaching and deactivation especially after several runs of
catalytic reaction. A powerful solution to this challenge is to prepare a mixture between
SBA-15 and the desired oxide catalyst;25 this is in fact a compromise between activity
and recoverability. Many other systems and materials have been prepared similarly for a
variety of applications.26-29 In the present study, Cu/SBA-15 has been synthesized and
characterized as an efficient and recyclable catalyst for the synthesis of some new aryl
diazenyl chromeno[2,3-d]pyrimidine derivatives 8 (Scheme 1).
Scheme 1

Chromenopyrimidine Azo-Dyes
345
Table 1
The Effects of Using Cu Based Catalysts for the Synthesis of Azo-Dye 8a in EtOH
Entry
Catalyst
Time (h)
Yield for 8a in EtOH (%)
1
2
3
4
5
6
7
8
—
—
1
3
15
20
40
35
22
25
50
80
—
24
3
CuO (bulk)
Cu(NO3)2
CuCl
3
3
Cu/SBA-15
Cu/SBA-15
1
3
Azo-dyes 8 can be produced with low yields in the presence of Lewis acids by the
reaction of aryl azo-salicylaldehyde 5 and 3-cyano iminocoumarins 7 (Scheme 1). In
order to improve the yields and optimize the procedure, various Lewis acids were tested;
copper salts proved to have the best activity; but the final product yields were still unsatis-
factory. Following our recent research using nano-catalysts,30,31 we tried to use copper-
based nano-catalysts. A model reaction was carried out for the synthesis of 8a using some
copper nano-catalysts. The yields of 8a for each one of the catalysts are presented in
Table 1. As can be seen, Cu/SBA-15 showed the best catalytic activity for the present
procedure. To optimize the reaction conditions, some solvents were investigated and
EtOH proved to be the most suitable, although MeOH was also acceptable (Table 2).
To optimize the amount of catalyst, we examined different ratios of Cu/SBA-15; 20
mol% proved to be optimal. Lowering this amount decreased the reaction yield but
increasing it did not have any beneficial effect. Therefore we report the newly synthesis
compounds 8a-j using 20 mol% Cu/SBA-15 as catalyst and EtOH as solvent.
The appearances of azo-dyes 8a-j, the chemical structures and their related final
yields are shown in Table 3.
1
The structures 8 were assigned on the basis of their elemental analysis, IR, H, 13C
NMR and mass spectral data, as shown in the Experimental Section. Single crystals of 8c
were obtained by crystallization from chloroform. The X-ray data were obtained to con-
firm unambiguously the proposed structure (Figure 1). Bragg-intensities of 8c were mea-
ꢀ
sured at low temperature [100(1) K], using Cu Ka radiation (1.54184 A) on a Rigaku
SuperNova dual diffractometer system equipped with an Atlas CCD detector. The dataset
was reduced and then corrected for absorption with CrysAlisPro.32 Solution and refine-
ment of the structure were performed by SHELXT33 and SHELXL-2016 (release 4),34
Table 2
The Effects of Using Cu/SBA-15 as Catalyst for the Synthesis of Azo-Dye 8a in Different
Solvents
Solvent
Yield without cat. (%)
Yield with Cu/SBA-15 (%)
EtOH
40
35
80
65
30
30
MeOH
CH2Cl2
Toluene
20
<10

346
Zonouzi et al.
Table 3
The Structure, Appearance, and Yields of Azo-Dye Compounds 8a-j
8
Y %
80
Structure
App.
a
b
c
78
74
d
78
e
f
70
70
g
70
(Continued on next page)

Chromenopyrimidine Azo-Dyes
347
Table 3
The Structure, Appearance, and Yields of Azo-Dye Compounds 8a-j (Continued)
8
Y %
70
Structure
App.
h
i
75
70
j
respectively. All non-hydrogen atoms were refined anisotropically using full-matrix least-
squares based on F2. The hydrogen atoms were placed in calculated positions by means of
the “riding” model, except the hydroxyl-hydrogen which was located in a difference map
and refined isotropically. The structure contains one third of a chloroform molecule; there
exist two disordered positions linked by the c glide plane to form an endless chain along
the c axis (shown in Figure 2). This disorder was taken care of by means of a ‘PART -1’
environment. The molecules of 8c are stabilized by an intramolecular O1-H¢¢¢¢¢¢N3 hydro-
gen bond (shown as dotted line in Figure 1, 2) between the O1ÀÀH group ofꢀaryl ring and
ꢀ
N3 atom ofꢀpyrimidine ring d (O1ÀÀN3 D 2.601(3) A, d (O1ÀÀH) D 0.91(4) A, d (HÀÀN3)
D 1.75(4) A, < O2ÀÀHÀÀN1 D 155(4)ꢀ. The molecules in the unit cell are interlinked by
van der Waals forces.
The UV-Visible spectra of compounds 8a-j were obtained (10¡5 mol/Lit) in CHCl3.
The spectra all show similar λmax. The UV-Vis spectra of compounds 8a-d (containing
piperidine) have been shown in Figure 3 (a) and for the compounds 8e-j (containing mor-
pholine) are shown in part b.
We now include specific data for the characterization of the catalyst. We believe
these data will be helpful in understanding the effectiveness of the new catalyst.
Low angle powder x-ray diffraction (Figure 4a) clearly shows the characteristic
peak of SBA-15 phase and regular XRD (Figure 4b) shows the characteristic peaks
of CuO (reference code 01-080-1268) with a scale factor of 0.937 and 0.000 degrees
displacement in 2u. Field-emission scanning electron micrographs (Figure 5) reveal

348
Zonouzi et al.
Figure 1 Molecular structure of 8c shown with 50% probability thermal ellipsoids.
the micron-scale morphology and structural homogeneity of the synthesized mesopo-
rous sample.
N2-physisorption analysis at 77k revealed type IV isotherms (Fig. 6). The BET sur-
face area was found to be 231 m2/g, total pore volume at p/p0 D 0.990 was 0.433 cm3/g
and the average pore diameter was 7.486 nm. The BJH diagram (insert of Figure 6)
shows uniform pore size distribution with a peak at 3.53 nm.
The easily recovered catalyst from the synthesis of compound 8a was used success-
fully four times for the same reaction without any significant loss in the product yield
(Figure 7).
In summary, the synthesis of some new stable azo-dye chromenopyrimidine deriva-
tives is accomplished by a simple approach using Cu/SBA-15 as catalyst. Azo-dyes 8a-j
possess yellow to reddish brown hues and have been fully characterized. X-ray analysis
for the product 8c showed an intramolecular H-bonding which leads to higher stability
of this dye. The catalyst was synthesized using a sol-gel method and characterized using
low angle and regular powder XRD, FESEM and N2-physisorption. This catalyst can be
easily separated from the reaction mixture and reused several times in subsequent reac-
tions without significant loss in the yields of products. Further investigation of this
method is currently in progress to establish its scope and utility.
Experimental Section
Chemicals and solvents were obtained from Merck (Germany), Aldrich (US) and
Fluka (Switzerland) and were used without further purification. Column chromatog-
raphy was performed on silica gel (0.015-0.04 mm, mesh-size) and TLC on pre-
coated plastic sheets (25 DCUV-254), respectively. Melting points were measured on
a Barnstead Electrothermal melting point apparatus and are not corrected. Elemental
analysis for C, H and N were obtained using a Thermo Finnigan Flash EA1112
instrument. IR spectra were recorded on a Bruker EQUINOX 55 spectrophotometer

Chromenopyrimidine Azo-Dyes
349
Figure 2 The crystal packing diagram of 8c.
Figure 3 a) UV-Vis spectra of compounds 8a-d and b) UV-Vis spectra of compounds 8e-j in
CHCl3.

350
Zonouzi et al.
Figure 4 a) Low angle and b) regular powder X-ray diffraction patterns of Cu/SBA-15 sample
Figure 5 Field-emission scanning electron micrographs from Cu/SBA-15 at a) 100kX and b)
150kX.
as ATR method. UV-Vis spectra were measured using a PG Instruments T80C spec-
1
trophotometer. H NMR and 13C NMR spectra were determined in CDCl3 on Bruker
500 spectrometer and chemical shifts were expressed in ppm downfield from tetra-
methylsilane. Mass spectra were recorded on a Finnigan-MAT 8430 spectrometer at
an ionization potential of 70 ev. Low angle and regular powder X-ray diffraction
patternsꢀ were obtained on a Philips PW1730 (Holland) diffractrometer with CuKa(λ
D 1.54A) radiation. N2-physisorption isotherms were obtained at 77K on a Belsorp
(Japan) Mini II instrument. Field-Emission Scanning Electron Micrographs and ele-
mental maps (Cu, Si, and O) were obtained using a TSCAN (Czech Republic)
MIRA 3 instrument. Crystallographic data for the structure of compound 8c has
been deposited with the Cambridge Crystallography Data Center as supplementary
publication No. CCDC 1527912. These data can be obtained free of charge via
www.ccdc.com.ac.uk/data_request/cif

Chromenopyrimidine Azo-Dyes
351
Figure 6 Adsorption and desorption isotherms of Cu/SBA-15 for N2 at 77k. Insert: BJH diagram of
this sample.
Figure 7 Reusability of Cu/SBA-15 as the catalyst in the preparation 8a.
General Procedure for the Synthesis of Arylazo Salicylaldehydes (5)
5-Arylazo salicylaldehydes 5 were synthesized (Scheme 1) according to the reported pro-
cedure.35 To a magnetically stirred solution of aniline and its derivatives 4 (0.05 mol)
was slowly added 8 mL of HCl (37% aq) at about 0–5ꢀC. Then 20 mL of NaNO2 solution
(4 g in 20 mL H2O) was added to the above mixture and stirred for 30 min. At this stage,
an alkaline solution of salicylaldehyde (0.05 mol in aq NaOH (20%)) was added to the

352
Zonouzi et al.
reaction mixture and stirred for 2–3 h. The orange powders of compounds 5 were filtered
and washed by 10 mL cold distilled water several times.
General Procedure for the Synthesis of Imino-2H-chromene-3-carbonitriles (7).
Compounds 7 were synthesized according to our previously reported simple proce-
dure.19,20 To a magnetically stirred solution of malononitrile (0.66 g, 10 mmol) and sali-
cylaldehydes 6 (10 mmol) in EtOH (10 mL) was added triethylamine (2 mmol) and the
mixture stirred for 20 min at room temperature. The white to yellow powder of the imino-
coumarins 7 were filtered and washed with cold n-hexane.
General Procedure for the Synthesis of Chromenopyrimidine Azo-Dyes (8a-j)
To a magnetically stirred solution of compounds 5 (1 mmol) in EtOH (15 mL) was added Cu/
SBA-15 (20 mol%) and the mixture stirred for 10 min. Then 1 mmol of compounds 7 and
1.5 mmol of amine (piperidine or morpholine) were added and the result stirred at room tem-
perature. The progress of the reaction was monitored by TLC. The spot for products typically
appeared after 20 to 60 min; (compounds 8a-d had Rfꢁ0.7 and compounds 8e-j had Rfꢁ0.5
on silica gel, ethylacetate/n-hexane: 1/3). When the spot for compounds 5 (Rfꢁ0.9 on silica
gel, ethylacetate/n-hexane: 1/3) disappeared after 4–5 h, the precipitated products were centri-
fuged and washed by EtOH (5-8 mL). In order to separate the catalyst it was sufficient to dis-
solve the solid product in CHCl3 (5 mL). Cu/SBA-15 was insoluble in CHCl3 and could be
easily separated by centrifuge and recovered for further use (Figure 7). After removing the
CHCl3 under reduced pressure and recrystallization from CHCl3, the yellow to brown powder
of products 8a-j were obtained in good yields (70-80%). Spectroscopic data for compound 8a
are given below, and for all of the azo-dyes 8a-j they are summarized in Tables 4 and 5.
(E)-4-(2-(Phenyldiazenyl)-2-(4-piperidin-1-yl)-5H-chromeno[2,3-d] pyrimidin-2-yl)
phenol (8a)
Pale orange powder; mp 203–205ꢀC; IR KBr (nmax): 3200-3100 (O-H), 1591, 1569 (C D
1
N), 1548 (N D N), 1280, 1216, 1104, 1083 (C-O) cm¡1; H NMR (500 MHz, CDCl3,
Table 4
Formulas, mps, Colors, and Elemental Analysis of 8a-j
Elemental analysis found (calc)
Cmpd
Formula
mp (ꢀC)
Color
C
H
N
8a
8b
8c
8d
8e
8f
8g
8h
8i
C28H25N5O2 203–205 Pale orange
C29H27N5O3 199–200 Deep yellow
C29H26ClN5O3 195–196 Reddish orange 65.82 (65.97) 4.90 (4.96) 13.50 (13.26)
72.48 (72.55) 5.35 (5.44) 15.30 (15.11)
70.43 (70.57) 5.45 (5.52) 14.30 (14.19)
C31H31N5O3 200–202 Deep yellow
C27H23N5O3 207–208 Light brown
C27H22ClN5O3 217–218 Light yellow
C29H27N5O3 212–214 Light brown
C28H25N5O4 243–244 Light yellow
C30H29N5O4 235–237 Orange
71.42 (71.38) 5.86 (5.99) 13.52 (13.43)
69.62 (69.66) 5.03 (4.98) 15.21 (15.04)
64.81 (64.86) 4.52 (4.44) 14.32 (14.01)
70.43 (70.57) 5.59 (5.51) 14.24 (14.19)
67.77 (67.87) 5.14 (5.09) 14.35 (14.13)
68.70 (68.82) 5.61 (5.58) 13.44 (13.38)
63.41 (63.46) 4.50 (4.56) 13.32 (13.21)
8j
C28H24ClN5O4 215–216 Orange

Chromenopyrimidine Azo-Dyes
353

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Zonouzi et al.

Chromenopyrimidine Azo-Dyes
355

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Zonouzi et al.

Chromenopyrimidine Azo-Dyes
357
Me4Si) dH 1.74-1.80 (6H, m, CH2 of piperidine), 3.46-3.47 (4H, m, CH2 of piperidine),
3.92 (2H, s, CH2), 7.06-7.11, 7.19-7.25, 7.42-7.51, 7.79-7.80, 9.05 (12H, 4m, aromatic
protons), 13.97 (1H, brs, OH) ppm; 13C NMR (125 MHz, CDCl3, Me4Si) dC 24.31,
25.62, 49.52 (CH2 of piperidine), 25.41 (CH2), 97.76, 117.06, 118.44, 118.68, 119.45,
122.56, 124.41, 125.06, 127.22, 128.20, 128.92, 130.08, 145.63, 150.56, 152.86, 161.42,
163.28, 1665.20 (aromatic carbons); MS: 463, 379, 274, 182, 77, 57; Anal. Calcd for
C28H25N5O2; C, 72.55; H, 5.44; N, 15.11. Found: C, 72.48; H, 5.35; N, 15.30.
Acknowledgments
We thank the Research Council of the University of Tehran and PCRC for the financial
support.
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