Preparation, characterization and use of sulfonylbis(1,4-phenylene)bis(sulfamic acid) as an eco-benign, efficient, reusable and heterogeneous catalyst for the synthesis of mono- and bis-chromenes

Article abstract of DOI:10.1007/s13738-017-1128-7

Sulfonylbis(1,4-phenylene)bis(sulfamic acid) (SPSA) is easily prepared and recognized as a new heterogeneous catalyst by the reaction of 4,4′-sulfonyldianiline with chlorosulfonic acid. This reagent was used for the synthesis of the mono- and bis-chromene

Full text of DOI:10.1007/s13738-017-1128-7

J IRAN CHEM SOC
DOI 10.1007/s13738-017-1128-7
ORIGINAL PAPER
Preparation, characterization and use of sulfonylbis(1,4‑
phenylene)bis(sulfamic acid) as an eco‑benign, effcient,
reusable and heterogeneous catalyst for the synthesis
of mono‑ and bis‑chromenes
Nosrat O. Mahmoodi1 · Zahra Khazaei1 · Masoud Mohammadi Zeydi1
Received: 1 November 2016 / Accepted: 21 April 2017
© Iranian Chemical Society 2017
Abstract Sulfonylbis(1,4-phenylene)bis(sulfamic
acid)
because they can produce the purpose products in single
proceeds without isolating the intermediates, thus reduc-
ing reaction times, waste production and energy consump-
tion. MCRs have suitability over conventional linear type
syntheses in numerous aspects including possible structural
variations, simple procedures and rapid access to com-
plex molecules. Hence, discovery and development of new
MCRs is highly favorable. One such reaction is the synthe-
sis of chromene derivatives [1–4].
(SPSA) is easily prepared and recognized as a new hetero-
geneous catalyst by the reaction of 4,4′-sulfonyldianiline
with chlorosulfonic acid. This reagent was used for the
synthesis of the mono- and bis-chromene derivatives. All
reactions were performed under mild reaction conditions in
high to excellent yields. The advantages of using the SPSA
as a heterogeneous catalyst in these reactions are: being
environmentally friendly, low cost, commercially availabil-
ity and easy to separate from the mixture of the reaction
and high reusable catalyst. Using this catalyst, results in
acceptable reaction time and high yields with high purity
of the obtained products without utilizing any organic sol-
Chromenes play an important role in the medicinal indus-
try as a principal skeleton for the plan of a number drug [5,
6]. Chromene derivatives have received considerable inter-
est from the medical industry due to their extensive range of
interesting biological and therapeutic properties, such as anti-
tumor [7], antimalarial [8, 9], antimicrobial [10, 11], anti-HIV
[12], anti-tubercular [13], anti-infammatory [14], analgesic
[15], antitumor [16], antifungal [17], antiparkinsonian agents
[18] and use as a retinoic acid receptor alpha antagonist lead
compound [19]. In addition, chromenes are presented in
numerous of the bioactive natural products [20]. Moreover,
some of chromenes are commonly employed as potential bio-
degradable agrochemicals, cosmetics and as pigments [21].
Lately, different combinations of chromene are designed
to have various biological activities, including anti-infam-
matory, anti-proliferative, anti-rheumatic, antibacterial,
anti-allergic, anti-cancerous, anti-tubercular and apoptosis-
inducing activities [22–24]. Because of these widespread
activities, their synthesis was continually the subject of
much research and is still pursued due to new emerging
methods, such as microwave heating. Performing reactions
under microwave irradiation frequently gives rise to rate
improvement and enhancement of yields. Microwave irra-
diation conditions are excellent suited to the so-called sol-
vent-free reactions. These reactions are eco-friendly and, in
sight of green chemistry’s desire to avoid solvent hazards,
1
vents. The catalyst was characterized by FT-IR, H NMR,
13C NMR, mass and TGA studies. All the products were
1
characterized by FT-IR, H, 13C NMR, HRMS, melting
point and elemental analyses.
Keywords 4,4′-Sulfonyldianiline · Chlorosulfonic acid ·
Chromene · Heterogeneous · Eco-benign
Introduction
The multi- or three-component, one-pot reactions (MCRs)
have attracted notable attention in organic synthesis
Electronic supplementary material The online version of this
article (doi:10.1007/s13738-017-1128-7) contains supplementary
material, which is available to authorized users.
* Nosrat O. Mahmoodi
mahmoodi@guilan.ac.ir
1
Department of Organic Chemistry, Faculty of Sciences,
University of Guilan, Rasht, Iran
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J IRAN CHEM SOC
are perfect. There are some methods for the synthesis
of chromenes using TBAF [25], DABCO [26], molecu-
lar iodine [27], TFE [28], potassium phosphate [29], rare
earth perfuorooctanoate [30], l-proline [31], TBAB [32],
IRA-400 (OH–) [33] and nanoparticles [34, 35] as catalyst.
Other condition such as ultrasound irradiations and micro-
wave irradiation is also reported for synthesis of these com-
pounds [36, 37]. However, most of these methods were lead
to preparation of monochromenes and have notable diff-
culty such as low yields of products, longer reaction times,
diffcult workup and harsh reaction conditions. Hence, the
development of simple, environmentally friendly, effcient,
high-yielding and clean approaches using some new cata-
lyst for the synthesis of these bis-compounds with alkyl
linkage is a momentous task. Application of heterogene-
ous acid catalyst in chemical transformations is important
because they have several advantages including recycling
of the catalyst, ease of products separation and environ-
mental acceptability as competition to liquid acid catalysts.
Heterogeneous acid has been used as catalysts for numer-
ous organic reactions. They are not only useful in terms of
selectivity and yield but also concerning the effuent pollu-
tion and workup [38–41]. To our knowledge, there has been
very little report on the use of heterogeneous acid as a solid
catalyst under microwave irradiation and solvent-free reac-
tion conditions in the synthesis of chromene derivatives. As
a result of our continuous research plans on the synthesis of
heterocyclic compounds, and in continuance of our previ-
ous works on the use of solid acid catalysts in organic reac-
tions, we here report that microwave-assisted condensation
of aromatic aldehyde 1 dimedone 2 with malononitrile 3
by using sulfonylbis(1,4-phenylene)bis (sulfamic acid), as
heterogeneous acid catalyst quickly prepared the chromene
derivatives (4a–j and 6a–e) in good yields (Scheme 2).
Scheme 1 Preparation of sulfonylbis(4,1-phenylene)bis(sulfamic
acid)
Scheme 2 Preparation of chromene derivatives in the presence SPSA
(Varian Medical Systems, Palo Alto, CA, USA). TGA anal-
yses were performed on Polymer Laboratories TGA-PL
thermal analysis instrument (heating rate of 10 °C/min).
Elemental analyses were made by a Carlo-Erba EA1110
CNNO-S analyzer and agreed with the calculated values.
High-resolution mass spectra (HRMS) were recorded on
Agilent 6520 (QTOF) ESI-HRMS instrument.
General procedure for the preparation of sulfonylbis
(1,4‑phenylene)bis(sulfamic acid) (SPSA) (Scheme 1)
A 25-mL suction fask charged with a solution of 4,4′-sul-
fonyldianiline (2.843 g, 10 mmol) in dry CH2Cl2 (5 mL)
was equipped with a constant pressure-dropping funnel
containing 1.165 g chlorosulfonic acid (10 mmol) and a
gas inlet tube for conducting HCl gas over an adsorbing
solution, i.e., water. Chlorosulfonic acid was added drop
wise over a period of 20 min, while the reaction mixture
was stirred slowly in an ice bath. The mixture was then
heated to room temperature and stirred for additional 2 h.
The mixture was fltered, and the solid residue was washed
with ether (3 × 5 mL) and dried under vacuum. SPSA was
obtained as a white-colored solid, 3.119 g (95% yield).
Experimental
Chemicals and reagents
All chemicals were available commercially and used with-
out additional purifcation. In all cases the products were
identifed by their spectroscopic properties and comparison
with authentic samples. All reactions were carried out in
a CEM MARS 5™ microwave oven. Melting points were
recorded on an electrothermal-type 9100 melting points
apparatus. The IR spectra were obtained using a 4300 Shi-
Spectral data of SPSA catalyst
White-colored solid: M.p. 244–248 °C; FT-IR (KBr):
3424, 2412–3378, 3123, 1632, 1589, 1277, 1143 cm−1
;
1
madzu spectrophotometer as KBr disks. H and 13C NMR
1H NMR (400 MHz, DMSO-d6): δ(ppm) 6.85 (d, 4H,
J = 8.8 Hz, 2CH), 7.61 (d, 4H, J = 8.8 Hz, 2CH), 7.95
(s, 2H, 2OH), 10.92 (s, 2H, 2NH); 13C NMR (100 MHz,
spectra were recorded with Bruker DRX500 spectrometers.
Mass spectra were obtained on a Varian Mat CH-7 at 70 eV
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J IRAN CHEM SOC
CDCl3): δ(ppm) 118.6, 129.6, 133.7, 146.9. MS: (70 eV),
m/z = 409 (M+ + 1), 408 (M+), 407 (M+–H), 406
(M+–2H), 327 (M+–SO3H), 248 (M+–2SO3H), 248 (dap-
sone), 64 (–SO2–).
(calcd. 660.7715 for C39H40N4O6): Anal.Calcd.for: C,
70.89; H, 6.10; N, 8.48. Found: C, 70.91; H, 6.13; N, 8.46.
4,4′‑((Butane‑1,4‑diylbis(oxy))bis(4,1‑phenylene))
bis(2‑amino‑7,7‑dimethyl‑5‑oxo‑5,6,7,8‑tetrahy‑
dro‑4H‑chromene‑3‑carbonitrile) (6b) (Table 3, entry 2)
General procedure for synthesis of chromenes 4a–j
catalyzed by SPSA (Scheme 2)
White powder, yield 98%, FT-IR (KBr): 3396, 3321,
3211, 2937, 2865, 2194, 1658, 1604, 1508, 1367,
1
A mixture of aromatic aldehyde (1 mmol), dimedone
(1 mmol), malononitrile (1 mmol) and SPSA (15 mol%)
was placed in a 50-ml beaker. The beaker was covered with
a stem less funnel and then irradiated in the microwave
oven for 5–15 min with power of 210 W. The progress of
reaction was monitored by TLC [n-hexane–EtOAc (3:1)].
After completion of the reaction, residue was dissolved in
hot EtOH. The solid catalyst was fltered off, and the fairly
pure crystals of products that separated on cooling from the
fltrate solution were further recrystallized in EtOH.
1213 cm−1; H NMR (400 MHz, DMSO-d6): δ (ppm)
0.96 (s, 3H, CH3), 1.05 (s, 3H, CH3), 1.85 (br, 2H, CH2),
2.10 (d, 1H, J = 16.0 Hz, CH), 2.26 (d, 1H, J = 16.0 Hz,
CH), 3.99 (br, 2H, CH2), 4.12 (s, 1H, CH), 6.85 (d,
2H, J = 8.0 Hz, 2CH), 6.98 (s, 2H, NH2), 7.05 (d, 2H,
J = 7.6 Hz, 2CH); 13C NMR (400 MHZ, DMSO-d6): δ
(ppm) 25.9, 27.2, 28.9, 32.2, 35.2, 50.5, 59.0, 67.5, 113.5,
114.6, 120.2, 128.7, 137.2, 157.8, 158.8, 162.6, 196.1;—
HRMS ((+)-ESI): m/z = 674.7980 (calcd. 674.7985 for
C40H42N4O6): Anal.Calcd.for: C, 71.20; H, 6.27; N, 8.30.
Found: C, 71.24; H, 6.30; N, 8.28.
General procedure for synthesis of chromenes 6a–e
catalyzed by SPSA (Scheme 2)
4,4′‑((Pentane‑1,5‑diylbis(oxy))bis(4,1‑phenylene))
bis(2‑amino‑7,7‑dimethyl‑5‑oxo‑5,6,7,8‑tetrahy‑
dro‑4H‑chromene‑3‑carbonitrile) (6c) (Table 3, entry 3)
A mixture of bis-aldehyde (5a–e) (1 mmol), dimedone
(2 mmol), malononitrile (2 mmol) and SPSA (15 mol%)
was placed in a 50-ml beaker. The beaker was covered
with a stem less funnel and then irradiated in the micro-
wave oven for 5 min with power of 210 W. The progress of
reaction was monitored by TLC [n-hexane–EtOAc (4:2)].
After completion of the reaction, residue was dissolved in
hot EtOH. The solid catalyst was fltered off, and the fairly
pure crystals of products that separated on cooling from the
fltrate solution were further recrystallized in EtOH.
White powder, yield 90%, IR (KBr): 3394, 3322; 3210,
2953, 2871, 2193, 1659, 1604, 1508, 1367, 1214 cm−1; 1H
NMR (400 MHz, DMSO-d6): δ (ppm) 0.95 (s, 3H, CH3),
1.04 (s, 3H, CH3), 1.55–1.57 (m, 1H, CH), 1.73–1.78
(m, 2H, 2CH), 2.10 (d, 1H, J = 16 Hz, CH), 2.25 (d, 1H,
J = 16 Hz, CH), 3.95 (t, 2H, J = 6.4 Hz, CH2), 4.12 (s,
2H, 1CH), 6.84 (d, 2H, J = 8.4 Hz, 2CH), 6.98 (s, 2H,
NH2), 7.04 (d, 2H, J = 8.4 Hz, 2CH); 13C NMR (400 MHZ,
DMSO-d6): δ (ppm) 22.7, 27.2, 28.8, 28.9, 32.2, 35.2, 50.4,
58.9, 67.7, 113.4, 114.6, 120.3, 128.6, 137.1, 157.8, 158.8,
158.9, 162.5, 196.1;—HRMS ((+)-ESI): m/z = 688.8250
(calcd. 688.8247 for C41H44N4O6): Anal.Calcd.for: C,
71.49; H, 6.44; N, 8.13. Found: C, 71.52; H, 6.42; N, 8.17.
4,4′‑((Propane‑1,3‑diylbis(oxy))bis(1,4‑phenylene))
bis(2‑amino‑7,7‑dimethyl‑5‑oxo‑5,6,7,8‑tetrahy‑
dro‑4H‑chromene‑3‑carbonitrile) (6a) (Table 3, entry 1)
White powder: yield 93%; FT-IR (KBr): 3384, 3331, 3212,
2959, 2872, 2193, 1677, 1603, 1508, 1368, 1214 cm−1; 1H
NMR (400 MHz, DMSO-d6): δ (ppm) 0.95 (s, 3H, CH3),
1.04 (s, 3H, CH3), 2.08–2.17 (m, 3H, CH), 2.25 (d, 1H,
J = 16.4 Hz, CH), 4.09 (t, 2H, J = 6.2 Hz, CH2), 4.12
(s, 1H, CH), 6.87 (d, 2H, J = 8.8 Hz, CH), 6.98 (2H, s,
NH2), 7.05 (d, 2H, J = 8.8 Hz, 2CH); 13C NMR (400 MHZ,
DMSO-d6): δ (ppm) 27.2, 28.8, 28.9, 32.2, 35.2, 50.4,
56.3, 64.6, 113.4, 114.7, 120.2, 128.7, 137.3, 157.6, 158.8,
158.9, 162.5, 196.1;—HRMS ((+)-ESI): m/z = 660.7710
4,4′‑((Hexane‑1,6‑diylbis(oxy))bis(4,1‑phenylene))
bis(2‑amino‑7,7‑dimethyl‑5‑oxo‑5,6,7,8‑tetrahy‑
dro‑4H‑chromene‑3‑carbonitrile) (6d) (Table 3, entry 4)
White powder, yield 98%, IR (KBr): 3399, 3325, 3212,
2958, 2872, 2194, 1657, 1604, 1508, 1367, 1215 cm−1; 1H
NMR (400 MHz, DMSO-d6): δ (ppm) 0.95 (s, 3H, CH3),
1.04 (s, 3H, CH3), 1.46 (br, 2H, CH2), 1.72 (br, 2H, CH2),
2.11 (d, 1H, J = 8.4 Hz, CH), 2.25 (d, 1H, J = 16 Hz,
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J IRAN CHEM SOC
CH), 3.93 (t, 2H, J = 6.6 Hz, CH2), 4.12 (s, 2H, 1CH),
6.84 (d, 2H, J = 8.4 Hz, 2CH), 6.98 (s, 2H, NH2), 7.04 (d,
2H, J = 8.4 Hz, 2CH). 13C NMR (400 MHZ, DMSO-d6): δ
(ppm) 22.7, 27.2, 28.8, 28.9, 32.2, 35.2, 50.4, 58.9, 67.7,
113.4, 114.6, 120.3, 128.6, 137.1, 157.8, 158.8, 158.9,
162.5, 196.1;—HRMS ((+)-ESI): m/z = 702.8520 (calcd.
702.8524 for C42H46N4O6): Anal.Calcd.for: C, 71.77; H,
6.60; N, 7.97. Found: C, 71.79; H, 6.58; N, 7.93.
4,4′‑(((1,4‑Phenylenebis(methylene))bis(oxy))bis(4,1‑phe
nylene))bis(2‑amino‑7,7‑dimethyl‑5‑oxo‑5,6,7,8‑tetrahy‑
dro‑4H‑chromene‑3‑carbonitrile) (6e) (Table 3, entry 5)
Scheme 3 Preparation of bis-chromenes reaction from reaction bis-
aldehydes, malononitrile and dimedone
White powder, yield 95%, IR (KBr): 3458, 3313, 3192,
2962, 2878, 2195, 1668, 1596, 1366, 1209 cm−1 1H
;
NMR (400 MHz, DMSO-d6): δ (ppm) 0.97 (s, 3H, CH3),
1.04 (s, 3H, CH3), 2.11 (d, 1H, J = 16.4 Hz, CH), 2.26
(d, 1H, J = 9.33 Hz, CH), 4.16 (s, 1H, CH), 5.06 (q, 2H,
J = 9.33 Hz, 2CH), 6.74–6.76 (m, 2H, 2CH), 6.86–6.88 (m,
1H, CH), 7.03 (s, 2H, NH2), 7.22 (t, 1H, J = 8.4 Hz, CH),
7.47 (s, 2H, 2CH);—HRMS ((+)-ESI): m/z = 722.8420
(calcd. 722.8423 for C44H42N4O6): Anal.Calcd.for: C,
73.11; H, 5.86; N, 7.75. Found: C, 73.15; H, 5.83; N, 7.77.
Catalyst characterization
To initiate our study, SPSA was straightforwardly prepared
by addition of two equivalents of chlorosulfonic acid to
4,4′-sulfonyldianiline (SP). The reaction is easy and clean
and after completion was separated. The structure of SPSA
catalyst was identifed by FT-IR, H, 13C NMR, TGA and
1
mass spectra.
Figure 1 presents the FT-IR spectra of dapsone (a) and
SPSA (b). The presence of an additional sulfonic acid
group on the dapsone nitrogens in SPSA increases the
number of vibrational modes and causes completely differ-
ent FT-IR spectrum. In the case of SPSA, the broad band
between 2100 and 3350 cm−1 that centered at 2807 cm−1
can be attributed to the -OH stretching of the -SO3H group.
SPSA displayed other specifc absorption bands at 1247,
1160, 1021 and 886 cm−1, which are defned to the asym-
metric and symmetric SO2 stretching, S-OH bending and
symmetric S–N stretching vibrations, respectively [47].
Alternatively, in the IR spectra of SPSA, the bands at 3333
Results and discussion
The preparation of remarkable chemical under environ-
mentally friendly conditions represents a challenging tar-
get in the tendency of organic chemistry. Recently, this
method has had a great development, mainly due to the
application of solid acids. In addition the development of
heterogeneous catalysts for organic synthesis has become a
major region of research. The possible advantages of these
systems over homogeneous materials could lead to novel,
environmentally benign chemical procedures for industry.
In continuation of our ongoing research program on the
development of new methods for the synthesis of heterocy-
clic derivatives [42–46], Here, we have described the prep-
aration of (sulfonylbis(1,4-phenylene))bis(sulfamic acid)
(Scheme 1) and its use as an inexpensive catalyst for syn-
thesis of mono‑ and bis-chromenes. The solvent-free reac-
tion was accomplished from condensation reaction of vari-
ous aromatic aldehydes, dimedone and malononitrile under
microwave irradiation (Schemes 2, 3).
and 3362 cm−1 disappeared and a band at 3425 cm−1
,
related to the –NH stretching of the –NHSO3H group,
emerged.
The 1H and 13C NMR spectra of the SPSA cata-
lyst obtained in DMSO-d6 are displayed in Figs. 2 and
1
3. According to Fig. 2 the important peaks of H NMR
spectrum of SPSA were pertinent to the acidic hydrogen
(SO3H) and observed at 10.92 ppm, while the acidic hydro-
1
gen of ClSO3H is at 13.45 ppm, the H NMR spectra of
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J IRAN CHEM SOC
Fig. 1 FT-IR spectra of dapsone and SPSA
dapsone in DMSO-d6 are reported in the literature [48]. It
is noteworthy that dapsone is soluble in Et2O, while SPSA
is readily soluble in water. Also ClSO3H is readily soluble
in CH2Cl2, while SPSA is insoluble in CH2Cl2.
of catalyst observed in the range of 310–370 °C. The TGA
information affrms that the catalyst is stable at 180 °C.
The mass spectrum of the SPSA is shown in Fig. 3.
The important peaks of MS spectrum of the SPSA were
related to the 409 (M+ + 1), 408 (M+), 407 (M+–H), 406
(M+–2H), 327 (M+–SO3H), 248 (M+–2SO3H), 248 (dap-
sone) and 64 (SO2).
Figure 4 provides the TGA curves of SPSA catalyst
under nitrogen. The TGA curve of SPSA indicated a
weight loss below 100 °C which is corresponding to the
loss of the physically adsorbed water. SPSA is degraded
mainly by a three-stage process. The frst weight loss
observed in the range of 180–190 °C (Tmax = 186 °C),
attributed to the loss of sulfonic acid. The second weight
loss, started at 250 °C (240–260 °C), can be due to the
thermal decomposition of the SO2 groups. The third
weight loss is corresponding to the complete destruction
Preparation of mono‑ and bis‑chromenes
After preparation and characterization of SPSA, catalytic
activity for the preparation of chromenes was checked.
For this principle, as a model reaction, the condensation of
4-chlorobenzaldehyde (1 mmol), dimedone (1 mmol) and
malononitrile (1 mmol) was carried out under microwave
irradiation at 210 W and solvent-free conditions by using
different quantities of SPSA. The results are summarized
in Table 1. Excellent results in the presence of SPSA were
obtained, while conversely in the absence of SPSA no prod-
uct was detected (Table 1, Entry 1). Raising the quantity of
the catalyst increased the yield of 4a. The optimal amount of
the catalyst was 15 mol%, the higher amount of the catalyst
beyond this value did not increase the yield of 4a noticeably.
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J IRAN CHEM SOC
Fig. 2 1H NMR and 13C NMR
spectra of SPSA
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Fig. 3 Mass spectra of SPSA
Fig. 4 TGA curves (up) of SPSA
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Table 1 Effect of the amount of the catalyst on the model reaction
Table 2 Synthesis of chromene derivatives 4a–j
Entry
Catalyst (mol%)
Time (min)
Yield (%)a
Entry Producta
Time
(min)
Yield
(%)b
M.p. (°C)
Found
Reported [ref]
1
2
3
4
5
Non
5
100
15
13
10
10
–
87
92
98
97
1
12
10
10
92
96
98
229–231 230–232 [49]
211–214 213–215 [49]
210–213 212–213 [50]
10
15
20
2
3
1 mmol 4-chlorobenzaldehyde, 1 mmol malononitrile, 1 mmol dime-
done and 15 mol% SPSA, under solvent-free and microwave irradia-
tion conditions at 600w
b
Isolated yield
Based on the result, this procedure was then extended
to variety of aldehydes and bis-aldehydes at the optimized
system. In all cases, aromatic aldehydes with substituents
electron withdrawing reacted better then aromatic alde-
hydes with substituents with electron-donating groups and
gave the expected products in high yields in rather short
reaction time. The results are summarized in Table 2 and 3.
4
5
10
15
95
92
205–206 200–203 [50]
198–199 198–200 [51]
Recycling and reusing of catalyst
The reusability of the catalyst was checked via the same
model reaction under optimized conditions. After comple-
tion of the reaction, the catalyst was fltered, washed with
EtOH, dried and reused for the same reaction process. As
shown in Fig. 5, the catalyst could be reused at least four
times with only little reduction in the catalytic activity of
the catalyst.
In order to display the suitability of the catalyst, we have
compared synthesis of chromene in the presence of SPSA
with some other catalysts for the similar reaction (Table 4).
Lack of compatibility with the environment, longer reac-
tion times, lower yields and higher temperature of other
methods make our system a better choice.
6
7
8
8
97
96
96
222–224 223–224 [51]
207–210 211–214 [49]
173–175 170–172 [50]
10
5
9
15
15
90
91
209–211 204–205 [51]
216–218 218–220 [50]
Conclusion
10
In conclusion, we have successfully developed a very eff-
cient, simple and mild methodology for the preparation of a
wide variety of bis-chromenes through reaction of aromatic
aldehyde, dimedone and malononitrile using SPSA as the
recyclable heterogeneous catalyst under solvent-free and
microwave irradiation conditions for the frst time. Other
advantages of this protocol are excellent yields, short reac-
tion time, no side reactions, simple preparation and han-
dling of the catalyst, easy workup and omitting any volatile
and hazardous organic solvents.
1 mmol aromatic aldehydes, 1 mmol malononitrile, 1 mmol dime-
done and 15 mol% SPSA, under solvent-free and microwave irradia-
tion conditions at 600w
a
All the products were characterized by comparison of their spec-
troscopic and physical data with authentic samples synthesized by
reported procedures
b
Isolated yield
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Table 3 Synthesis of novel bis-
chromene 6a–e
Entry
1
Producta
Time (min)
12
Yield (%)b
93
M.p. (°C)
171–173
2
3
4
5
10
10
12
10
98
94
98
95
183–185
216–218
239–242
204–207
1 mmol bis-aldehyde, 2 mmol malononitrile, 2 mmol dimedone and 15 mol% SPSA, under solvent-free
and microwave irradiation conditions at 600w
a
All the products were characterized by comparison of their spectroscopic and physical data with authen-
tic samples synthesized by reported procedures
b
Isolated yield
Table 4 Comparison of the synthesis of chromene in the presence of
SPSA with some other catalysts
Time (min)
Yiled (%)
110
Entry Catalyst/solvent/condition
Time
(min)
Yield Refs.
(%)
105
10
12
1
2
3
4
5
6
7
8
9
TBAF/H2O/refux
30
60
94
94
88
95
80
93
75
85
98
[25]
12
16
100
95
DABCO/H2O/refux
I2/DMSO/80 °C
[26]
110
300
360
15
[27]
TFE/refux
[28]
96
98
RE(PFO)3/EtOH/60 °C
CA-SiO2/EtOH·H2O/refux
RuBr2(PPh3)4/MeOH/refux
SO24−/MCM-41/H2O/refux
SPSA/solvent-free/MW
[30]
95
90
85
93
[50]
12
[52]
step 1
step 2
step 3
step 4
30
[49]
10
This work
Fig. 5 Reusability of catalyst for model reaction
1 3

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