Mg(ClO4)2 as a recyclable catalyst for synthesis of 4H-chromenes

Article abstract of DOI:10.13005/ojc/320453

The 4H-choromen derivatives were obtained in excellent yield by three component of an aromatic aldehyde, dimedon and malonitril in the presence catalyst Mg(ClO₄)₂ as a lewis acid catalyst, in the conditions reflux. The advantage of this method addition to the resuble catalyst, high yield and easy method.

Full text of DOI:10.13005/ojc/320453

ISSN: 0970-020 X
CODEN: OJCHEG
2016, Vol. 32, No. (4):
Pg. 2215-2220
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
Mg(ClO4)2 as a Recyclable Catalyst for
Synthesis of 4H-chromenes
MASOUd MOHAMMAdI ZEYdI1* and SOMAYEH AHMAdI2
1Department of Organic Chemistry, University of Guilan, University of campus 2, Rasht, Iran.
2Department of chemistry, Tonekabon Branch, Islamic Azad University, Tonekabon, Iran.
*Corresponding author’s E-mail Email: zedi.65@gmail.com
http://dx.doi.org/10.13005/ojc/320453
(Received: June 30, 2016; Accepted: August 05, 2016)
AbSTRACT
The 4H-choromen derivatives were obtained in excellent yield by three component of an
aromatic aldehyde, dimedon and malonitril in the presence catalyst Mg(ClO4)2 as a lewis acid catalyst,
in the conditions reflux.The advantage of this method addition to the resuble catalyst, high yield and
easy method.
Keyword: 4H-choromen, aromatic aldehyde, dimedon and malonitril.
INTROdUCTION
DBU17, SiO2-Pr-SO3H18, boric acid19, Piperidine20,
MgO21, CuO-CeO2 nanocomposite22, CeCl3.H2O23,
Methane Sulphonic Acid24 Potassium Phosphate25,
and different energy sources such as ultrasonic
irradiation26, microwave-irradiation27,28, ionic liquid29
and Grinding30.Recently, a catalyst free method was
reported for the synthesis of chromene derivatives in
water31. In the study, we report Mg(ClO4)2 as a new
lewis acid catalyst for the three component synthesis
of 4H-chromene derivatives under conditions
reflux.
4H-chromenes are important heterocyclic
structural with a number of biological and
pharmacological properties including anti-cancer1,
anti-tumor2, anti-proliferative3, antidiabetic4, anti-
viral5, and anti-microbial6, antidepressant7, activities.
They have also been widely employed as pigments,
cosmetics8,andpotentbiodegradableagrochemicals9.
Substituted 4H-chromene derivatives are potent
apoptosis in ducting agents possessing vascular
disrupting activity10.
RESULTS ANd dISCUSSION
In recent years new method have been
developed for the synthesis of 4H-choromen
derivatives using various reagents such ammonium
Mg(ClO4)2 were tested as the catalyst in the
synthesis of 2-amino-7,7-dimethyl-5-oxo-4-phenyl-
5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile
salts11-14, amino functionalized silica gel15, K2CO316
,

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ZEyDI & AHMADI, Orient. J. Chem., Vol. 32(4), 2215-2220 (2016)
4a (Figure 1). At the start of this investigation, the examined under UV 254 and 365 nm light. Infrared
one-pot three component reaction of benzaldehyde spectra (µ/cm-1) were recorded on a Shimadzu IR-
1a, malononitrile 2 and dimedon 3 (1 mmol each) 470, using KBr disks. 1H spectra were recorded on
in ethanol was employed as a model reaction. The a DRX-400 MHz NMR Spectrometer at 293 K in
use of different amounts of catalyst (10, 20, 25, and CDCl3. Spectra were internally referenced to TMS.
30W %) at different temperature was investigated. Peaks are reported in ppm downfield of TMS.
The best result was obtained with 25W% of starch
solution at 100°C (Tables 1, Enter 11).
General procedure for the one-pot preparation
of 2-amino-7,7-dimethyl-5-oxo-4-phenyl-5,6,7,8-
The model reaction was carried out in tetrahydro-4H-chromene-3-carbonitrile(4a-l)
different solvent such as water, ethanol, methanol, To a mixture of aldehydes aromatic (1 mmol)
chloroform acetonitrile in the conditions reflux and in ethanol (5 ml) was added a malononitril(1 mmol),
so solvent free condition at 100°C using 25 W% of dimedone (1 mmol) and Mg(ClO4)2 (25 mol%). The
Mg(ClO4)2 as catalyst (table 2). Further, we studied reaction mixture was stirred for appropriate time
model reaction in water gave the highest yield (87%) as given table 4. After completion of the reaction
of 4a at reflux condition (tables 2, Enter 2).
(monitored by TLC), Mg(ClO4)2 was filtered out
using filter paper.Then, the solvent of the filtrate was
To study the recyclability of the catalyst, evaporated and the crude product was purified by
the Mg (ClO4)2 were used for the same reaction recrystallization from hot ethanol.The product were
repeatedly and the change in their catalytic activity characterized by the comparison of their spectral (1H
was studied.The relation between the number of the NMR of IR) and physical data with those reported in
reaction and the catalytic activity in terms of yield of the literature.
product is presented in table 3. The Mg(ClO4)2 can
be recycled and reused as a catalyst for at least four 2-amino-7,7-dimethyl-4-phenyl-5-oxo-5,6,7,8-
times without losing activity.
tetrahydro-4H-chronene-3-carbonitril (4a)
yellow Crystal. yield (90%), m.p .230-
After optimization of the reaction conditions, 232oC. FT-IR (Vmax/cm-1) (KBr disc): 3415, 3339
the scope and generality of these conditions with (NH2 Str.); 3050 (C-Harom Str.); 2990 (C-HaliPh Str.);
other reactants were examined by using a variety of 2243 (C°N Str.); 1686 (C=O Str.); 1215 (C-O Str.).
aromatic aldehydes, dimedon and malononitrile.The 1HNMR (400.13 MHz, CDCl3): d 1.05 (3H, s, CH3);
results are summarized in Table 4. All the reactions 1.13 (3H, s, CH3); 2.24 (2H, AB q, 3J = 16.4, 9.4 Hz,
proceeded smoothly under the optimized conditions CH2); 2.47 (2H, m, CH2); 4.42 (H, s, CH); 4.57 (2H,
and all the reactions were satisfactorily completed s, NH2); 7.19-7.32 (5H, m, CHarom).
within 2.5–3.5 hour.
2-amino-7,7-dimethyl-4-(3-nitrophenyl)-5-oxo-
In summary, a one-pot, three-component 5,6,7,8-tetrahydro-4H-chronene-3-carbonitril
condensation reaction of various aldehydes aromatic, (4b)
dimedon and malononitriles was successfully
yellow Crystall. yield (95%), m.p. 216-
accomplished to give 4H-chromene derivatives. 218oC.FT-IR (Vmax/cm-1) (KBr disc):3410, 3320 (NH2
This methodology has advantages of mild reaction Str.); 3032 (C-Harom Str.); 2900 (C-HaliPh Str.); 2256
conditions, simple experimentation, and high (C°N Str.); 1690 (C=O Str.); 1550, 1347 (N2O Str.).
yields.
1HNMR (400.13 MHz, CDCl3): d 1.06 (3H, s, CH3);
3
1.13 (3H, s, CH3); 2.25 (2H, ABq, J = 16.4, 10.4
3
Experimental materials and methods
Hz, CH2); 2.50 (2H, AB q, J = 16.8, 4.0 Hz, CH2);
Compounds were obtained from Merck 4.54 (H, s, CH); 4.79 (2H, s, NH2); 7.50-8.10 (4H,
and used without further purification. The melting m, 4CHarom).
points were obtained on an electro-thermal capillary
melting point apparatus and are uncorrected. Thin- 2-amino-7,7-dimethyl-4-(3-chlorophenyl)-5-oxo-
layer chromatography was performed using HF254 5,6,7,8-tetrahydro-4H-chronene-3-carbonitril
fluorescent silica gel plates (Merck), which were (4c)

ZEyDI & AHMADI, Orient. J. Chem., Vol. 32(4), 2215-2220 (2016)
2217
White Crystal, yield (93%), m.p. 220-
222°C.FT-IR (Vmax/cm-1) (KBr disc):3355, 3298 (NH2
Str.); 3120 (C-Harom Str.); 2956 (C-HaliPh Str.); 2186
(C°N Str.); 1651 (C°N Str.); 1215 (C-O Str.).1H NMR
(400.13 MHz, CDCl3): d 1.06 (3H, s, CH3); 1.13 (3H,
s, CH3);2.24 (2H, AB q, 3J = 16.4, 3.2 Hz, CH2);2.47
(2H, m, CH2); 4.40 (H, s, CH); 4.65 (2H, s, NH2);
7.17-7.28 (4H, m, 4CHarom).
(400.13 MHz, CDCl3): d 1.07 (3H, s, CH3); 1.13 (3H,
s, CH3); 2.25 (2H, ABq, 3J =16.4, 2.4 Hz, CH2); 2.46
(2H, m, CH2);3.80 (3H, s, CH3);4.39 (H, s, CH);4.57
(2H, s, NH2); 6.74-7.28 (4H, m, 4CHarom).
2-amino-7,7-dimethyl-4-(4-chlorophenyl)-5-oxo-
5,6,7,8-tetrahydro-4H-chronene-3-carbonitril
(4e)
White Crystal, yield (93%), m.p .215-
217°C. FT-IR (Vmax/cm-1) (KBr disc): 3371, 3303
(NH2 Str.); 3110 (C-Harom Str.); 2980 (C-HaliPh Str.);
2198 (C°N Str.); 1668 (C=O) Str.); 1217 (C-O Str.).
1H NMR (400.13 MHz, CDCl3): d 1.04 (3H, s, CH3);
1.13 (3H, s, CH3); 2.23 (2H, ABq, 3J =16.4, 7.2 Hz,
CH2); 2.47 (2H, s, CH2); 4.40 (H, m, CH); 4.58 (2H,
s, NH2); 7.18-7.29 (4H, m, CHarom).
2-amino-7,7-dimethyl-4-(3-methoxyophenyl)-5-
oxo-5,6,7,8-tetrahydro-4H-chronene-3-carbonitril
(4d)
White Crystal, yield (87%), m.p. 190-
193°C.FT-IR (Vmax/cm-1) (KBr disc):3379, 3301 (NH2
Str.); 3085 (C-Harom Str.); 2965 (C-HaliPh Str.); 2288
(C°N Str.);1670 (C=O) Str.);1219 (C-O Str.).1H NMR
O
R
R1
R2
H3C
O
3
O
CHO
CN
Mg(ClO4)2
CN
+
R2
R1
EtOH,reflux
H3C
O
NH2
CN
2
R
1a-h
4a-h
Fig. 1: Synthesis 4H-chromene under condition reflux
Table 2: Synthesis of 4H-chromenes
(4a) in different solvents
Table 1: Effect of quantity of Mg(ClO4)2 and
temperature on the synthesis of 4a
Enter
Solvent
Time (h) (%)Yield
Enter Quantity
(W%)
M.P.
(°C)
Time
(h)
Yield
(%)
1
2
3
4
5
6
Solvent-free
Water
Aqueous Ethanol
Methanol
3:30
3
3
3
3:30
3:30
45
63
87
83
51
54
1
2
3
4
5
6
7
8
……
……
10
10
10
20
20
20
25
25
25
30
30
.......
100
80
90
100
80
90
100
80
90
100
80
6
6
5
5
5
4
4
4
3
3
3
3
3
3
.......
33
35
38
42
39
43
42
63
82
87
78
80
80
Chloroform
Acetonitrile
Table 3: recyclability of catalyst for the
synthesis of 4H-chromene 4a
9
10
11
12
13
14
Number
Catalyst (g)
Yield (%)
1
2
3
4
0.057
0.055
0.051
0.045
87
85
82
72
90
100
30

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ZEyDI & AHMADI, Orient. J. Chem., Vol. 32(4), 2215-2220 (2016)
Table 4: synthesis of different 4H-chromene derivatives 4a-h catalyzed by Mg(ClO4)2
Enter
prodact
Ar
Time
(h)
Yield
(%)
M.p. (obsd)
M.p. (lit.)
(°C)
(°C)
4a
3
90
95
93
87
230-232
216-218
230-232
190-193
235-23715
209-21127
234-23632
——
O
CN
O
NH2
NO2
O2N
4b
4c
4d
2.3
2.3
3.3
O
CN
NH2
Cl
O
Cl
O
CN
O
NH2
OCH3
H3CO
O
CN
O
NH2
Cl
4e
4f
2:30
2.5
93
90
91
215-217
210-212
233-235
216-21831
214-21531
——
O
Cl
CN
O
NH2
Cl
O
Cl
CN
O
NH2
F
4g
2.3
O
F
CN
O
NH2
CH3
4h
3
89
213
208-21015
H3C
O
CN
O
NH2

ZEyDI & AHMADI, Orient. J. Chem., Vol. 32(4), 2215-2220 (2016)
2219
2-amino-7,7-dimethyl-4-(2-chlorophenyl)-5-oxo-
5,6,7,8-tetrahydro-4H-chronene-3-carbonitril
(4f)
(C°N Str.);1630 (C=O) Str.);1205 (C-O Str.).1H NMR
(400.13 MHz, CDCl3): d 1.06 (3H, s, CH3); 1.12 (3H,
s, CH3); 2.23 (2H, ABq, 3J =16.4, 5.6 Hz, CH2); 2.30
(3H, s, CH3); 2.46 (2H, s, CH2); 4.38 (H, s, CH); 4.55
(2H, s, NH2); 7.09-7.28 (4H, m, CHarom).
White Crystal, yield (90%), m.p. 205-
207 °C.FT-IR (Vmax/cm-1) (KBr disc):3320, 3272 (NH2
Str.); 3117 (C-Harom Str.); 2988 (C-HaliPh Str.); 2201
(C°N Str.);1688 (C=O) Str.);1215 (C-O Str.).1H NMR
(400.13 MHz, CDCl3): d 1.08 (3H, s, CH3); 1.12 (3H,
s, CH3); 2.22 (2H, ABq, 3J =16.4, 8.4 Hz, CH2); 2.47
(2H, s, CH2); 2.47 (2H, s, CH2); 4.67 (2H, s, NH2);
4.86 (H, s, CH); 7.13-7.34 (4H, m, 4CHarom).
CONCLUSIONS
We report a novel one pot three component
synthesis of functionalized 4H-chromene derivatives
in the presence of Mg(ClO4)2 as catalyst.This reaction
series was found to be highly effective under reflux
conditions. Mg(ClO4)2 is an effective catalyst and
provides a new and useful method for the synthesis of
pyrannulated heterocyclic systems by condensation
of arylaldehydes, dimedonand malononitrile. The
catalyst is environmentally friendly, inexpensive,
clean, safe, nontoxic, and easily obtained.Moreover,
the procedure offers several advantages including
high yields, clean reaction conditions, and no
pollution threat to the environment, which together
make a useful and attractive process for synthesis
of these compounds.
2-amino-7,7-dimethyl-4-(2-flourophenyl)-5-oxo-
5,6,7,8-tetrahydro-4H-chronene-3-carbonitril
(4g)
White Crystal, yield (91%), m.p. 233-
235°C.FT-IR (Vmax/cm-1) (KBr disc):3400, 3350 (NH2
Str.); 3045 (C-Harom Str.); 2950 (C-HaliPh Str.); 2210
(C°N Str.);1620 (C=O) Str.);1225 (C-O Str.).1H NMR
(400.13 MHz, CDCl3): d 1.06 (3H, s, CH3); 1.13 (3H,
s, CH3); 2.24 (2H, ABq, 3J =16.4, 5.6 Hz, CH2); 2.47
(2H, m, CH2); 4.42 (H, s, CH); 4.55 (2H, s, NH2);
7.21-7.32 (4H, m, 4CHarom).
2-amino-7,7-dimethyl-4-(4-methylphenyl)-5-oxo-
5,6,7,8-tetrahydro-4H-chronene-3-carbonitril
(4h)
White Crystal, yield (89%), m.p. 225-
227°C.FT-IR (Vmax/cm-1) (KBr disc):3435, 3330 (NH2
Str.); 3095 (C-HaromStr.); 2964 (C-HaliPh Str.); 2201
ACKNOWLEdGMENTS
The partial support of this research by
the Research Committee of the University of
tonekabon Islamic Azad University is gratefully
acknowledged.
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