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One-pot multicomponent reaction for the synthesis of 2-amino-4- chromenes

promoted by 1-methyl imidazoliumiodide [mim]Cl ionic-liq- uid catalyst under
solvent-free conditions

Article · January 2015

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Iranian Chemical Communication
Original Research Article

Payame Noor University of Ilam http://icc.journals.pnu.ac.ir

One-pot multicomponent reaction for the synthesis of 2-amino-4-

chromenes promoted by 1-methyl imidazoliumiodide [mim]Cl ionic- liq-
uid catalyst under solvent-free conditions

Mohammad Reza Poor Heravi*, Mohammad Reza Amirloo

Department of Chemistry, Payame Noor University, P.O. BOX 19395-4697 Tehran, Iran

Received: 17 July 2014, Accepted: 18 August 2014, Published: 18 August 2014

Abstract

A simple, clean, and environmentally benign three-component process for the synthesis of 2-
amino-4Hchromenes using [mim]Cl, as an efficient catalyst under solvent-free conditions are
described. A wide range of aromatic aldehydes would easily undergo condensations with 1-
naphthol and malononitrile under solvent-free conditions in order to afford the desired products
of good purity in excellent yields. Taking into account the environmental and economical con-
siderations, the protocol presented here has the merits of environmentally benign, simple opera-
tion, convenient work-up and good yields. Furthermore, the catalyst can be easily recovered and
reused for at least five cycles without losing its activities.

Keywords: Chromene, multicomponent reactions, 1-methyl imidazoliumiodide [mim]Cl, sol-

vent-free conditions

Introduction (MCRs) which are one of the best tools in the

synthesis of organic compounds [1]. Recently,
Another window of green chemistry to
MCRs have emerged as a highly valuable syn-
take into consideration is the development of
thesis tool in the context of modern drug dis-
the one-pot multi-component reactions

*Corresponding author: Mohammad Reza Poor Heravi

Tel number: +98 (242) 5226932; Fax number: +98 (242) 5224021 Iran. Chem. Commun. 3 (2015) 73-84
E-mail: [email protected]

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 M.R. Poor Heravi, M. R. Amirloo / Iranian Chemical Communication 3 (2015) 73-84

covery. The atom economy and convergent Some of them can also be employed as cos-
character, the simplicity of a one-pot proce- metics and pigments [3], and utilized as poten-
dure, the possible structural variations, the ac- tial biodegradable agrochemicals [4]. 2-
cessible complexity of the molecules, and the Aminochromenes are generally prepared by
very large number of accessible compounds refluxing malononitrile, aldehyde, and acti-
are among the described advantages of MCRs. vated phenol in the presence of hazardous or-
Thus, they are perfectly amenable to automa- ganic bases like piperidine in organic solvents
tion for combinatorial synthesis. such as ethanol and acetonitrile for several

The third issue to be addressed in the con- hours [5]. A literature survey revealed several

text of durable development and Green Che- modified procedures using cetyltrimethylam-

mistry is ionic- liquid catalyst. These concepts monium chloride (CTAC), [6] tetrabutylam-

are at the center of the chemical activity, and monium bromide (TBAB), [7] cetyltrimethy-

the research on high selectivity is the driving lammoniumbromide (CTAB) coupled with

force for the conception of all new catalytic ultrasound, [8] γ-alumina, [9] K2CO3, [10] na-

processes. At present, it is well known that an nosize MgO, [11] heteropolyacid, [12] hex-

ionic- liquid catalyst must have three characte- adecyltrimethylammonium bromide,

ristics: high activity, selectivity and stability (HTMAB), [13] triethylbenzylammonium

(separation, recovery, recycling). The ideas of chloride (TEBA), [14]

the new generation of catalysts should include ([PhCH2Me2N+CH2CH2NMe2]Cl) [15] and

these three aspects. TiCl4 [16, 17]. As part of our program aimed at
developing useful new selective and synthesis
2-Aminochromenes which represent an
methods based on the use of functionalized
important class of compounds can be consi-
ionic liquids as catalysts of fine chemical
dered as the main components of many natu-
preparation, we have studied using the MCR
rally occurring products, and have been of in-
strategy for the synthesis of substituted 2-
terest in recent years due to their useful biolog-
aminochromenes using the basic ionic liquid
ical and pharmacological aspects, such as anti-
catalyst, 1-methyl imidazoliumidide [mim]Cl,
coagulants, spasmolytic, diuretic, insecticide,
under solvent-free conditions.
anticancer, and antianaphylactin activity [2].

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 One-pot multicomponent reaction for the synthesis of 2-amino-4-chromenes promoted by …

Scheme 1. Preparation of 2-amino-4-aryl-4H-benzo[h]chromene-3-carbonitrile and 3-amino-1-aryl-1H-

benzo[f]chromene-2-carbonitrile using [mim]Cl (IL) as catalyst under solvent-free conditions

Experimental chine on a JMS-700 double focusing Mass

spectrometer (JEOL, Tokyo, Japan). The ionic
General
liquid was prepared according to the method
All reagents were purchased from Merck. 17
reported in the literature. All the reactions
Aldehydes were distilled before use. Melting
were monitored by TLC using 0.25 mm silica
points were detetmined in open capillaries us-
gel plates (Merck 60F254) UV indicator.
ing Melting Electrothemal X6 microscopy,
digital melting point apparatus. IR spectra General procedure for the synthesis of 2-

were recorded on a Bruker Equinox 55 spec- amino4-chromenes

trometer using KBr pellets. NMR spectra were An equimloar (4 mmol) mixture of an
recorded using a Brucker DRX500 machine at aromatic aldehyde (1), malononitrile (2), 1-
room temperature. 1H, 13C NMR and 19FNMR naphthol (3) and 10 mole% [mim]Cl was vigo-
spectra were measured using DMSO-d6 as sol- rously stirred at 80 C for the specific time in-
vent. CHN analyses were performed on Exeter dicated in Table 1. The end of the reaction was
Analytical Inc. 'Model C-400 CHN Analyzer'. monitored by TLC. Then, the crude product
Mass spectra were obtained using a Micro obtained was added to the distilled water. The
Mass LCT machine in EI mode. HRMS ma- resulting precipitated solid was filtered out and

Page | 75
 M.R. Poor Heravi, M. R. Amirloo / Iranian Chemical Communication 3 (2015) 73-84

purified by recrystallization from hot methanol 2-Amino-4-(naphthalen-2-yl)-4H-

to afford the pure products (4). The catalyst benzo[h]chromene-3-carbonitrile (4n)
remained in the water was reused at another 0.274g (92%); white solid; mp 256-257
cycle after evaporation of water. All of the o
C. IR (KBr): 3234, 3054, 2980, 2211, 1650,
products are known and the data are found to 1512, 1465, 1119, 810 cm-1. 1H NMR (DMSO-
be identical with those that reported in the lite- d6, 500 MHz): 4.75 (s, 1H, H-4), 6.85 (s, 2H,
rature (Table 2). NH2), 7.23 (d, 1H, H-5, J=8.0 Hz), 7.43-7.56
Characterization data of some representa- (m, 4H, Ar-H), 7.62-7.98 (m, 6H, Ar-H), 8.04
tive compounds: (d, 1H, H-7, J=8.0 Hz), 8.21 (d, 1H, H-7,
J=8.0 Hz). 13C NMR (DMSO-d6, 125 MHz): δ
2-Amino-4-(4-(trifluoromethyl)phenyl)-4H-
31.43, 60.42, 120.83, 121.54, 122.43, 122.58,
benzo[h]chromene-3-carbonitrile (4g)
123.54, 126.02, 126.28, 127.01, 129.06,
0.359g (98%); white solid; mp 212-214
130.35, 132.93, 133.76, 136.98, 137.96,
o
C. IR (KBr): 3387, 3121, 2971, 2219, 1651,
141.65, 143.54, 147.34, 151.54, 156.43. MS
1522, 1474, 1109, 802 cm-1. 1H NMR (DMSO-
(EI), m/z (%) =348 (M+, 15), 221 (75). HRMS
d6, 500 MHz): 4.86 (s, 1H, H-4), 6.79 (s, 2H,
(EI) Found: M+, 348.1301. C24H16N2O re-
NH2), 7.11 (d, 1H, H-5, J=8.0 Hz), 7.51-7.79
quires M+ , 348.1300. Anal Calcd for
(m, 4H, Ar-H), 7.80-7.88 (m, 3H, Ar-H), 7.91
C24H16N2O: C, 82.74; H, 4.63; N, 8.04;.
(d, 1H, H-7, J=8.0 Hz), 8.10 (d, 1H, H-7,
Found: C, 82.73, H, 4.65; N, 8.06.
J=8.0 Hz). 13C NMR (DMSO-d6, 125 MHz): δ
48.87, 59.42, 121.43, 122.54, 123.21, 123.98, 3-Amino-1-(4-(trifluoromethyl)phenyl)-1H-

124.54, 125.65, 126.32, 127.08, 128.21, benzo[f]chromene-2-carbonitrile (5g)

129.76, 130.54, 131.32, 133.83, 134.12, 0.358g (98%); white solid; mp 235-237
135.65, 136.09, 137.96 (q, 1JCF=255.76 Hz), o
C. IR (KBr): 3124, 3054, 2975, 2233, 1643,
19
147.34, 156.43. F NMR (DMSO-d6, 470 1523, 1455, 1143, 809 cm-1. 1H NMR (DMSO-
MHz): -110.8. MS (EI), m/z (%) =366 (M+, d6, 500 MHz): 5.34 (s, 1H, H-4), 6.79 (s, 2H,
35), 221 (83). HRMS (EI) Found: M+, NH2), 7.23-7.43 (m, 2H, Ar-H), 7.45-7.52 (d,
366.1003. C21H13F3N2O requires M+ , 2H, J=8.0 Hz, H-3,5), 7.60 (d, 1H, J=8.0 Hz,
366.1000. Anal Calcd for C21H13F3N2O: C, H-9), 7.63-7.75 (m, 2H, Ar-H), 7.78 (d, 1H,
68.85; H, 3.58; N, 7.65. Found: C, 68.89, H, J=8.0 Hz, H-10), 7.81-7.96 (d, 2H, J=8.0 Hz,
13
3.56; N, 7.67. H-2,6). C NMR (DMSO-d6, 125 MHz): δ

Page | 76
 One-pot multicomponent reaction for the synthesis of 2-amino-4-chromenes promoted by …

29.93, 58.92, 121.63, 122.74, 122.96, 123.88, 0.289g (85%); white solid; mp 251-253
o
123.96, 125.12, 125.98, 126.11, 129.11, C. IR (KBr): 3124, 3065, 2981, 2198, 1666,
131.65, 132.03, 132.86, 135.08, 137.06(q, 1544, 1451, 1107, 802 cm-1. 1H NMR (DMSO-
1
JCF=247.54 Hz), 140.55, 143.04, 148.34, d6, 500 MHz): 3.82 (s, 6H, 2×CH3), 5.43 (s,
153.50, 159.03. MS (EI), m/z (%) =366 (M+, 1H, H-4), 6.67 (s, 2H, NH2), 7.17-7.34 (m, 4H,
25), 221 (65). HRMS (EI) Found: M+, Ar-H), 7.47-7.54 (m, 3H, Ar-H), 7.56-7.67 (m,
366.1008. C21H13F3N2O requires M+ , 3H, Ar-H),. 13
C NMR (DMSO-d6, 125 MHz):
366.1001. Anal Calcd for C21H13F3N2O: C, δ 44.83, 56.93, 67.54, 119.03, 121.94, 122.43,
68.85; H, 3.58; N, 7.65. Found: C, 68.73, H, 122.43, 123.03, 124.42, 127.02, 128.54,
.61; N, 7.66. 129.68, 130.54, 132.33, 133.46, 134.78,
138.16, 143.95, 146.34, 148.04, 153.40,
3-Amino-1-(4-hydroxy-3-methoxyphenyl)-
158.52. MS (EI), m/z (%) =341 (M+, 17), 221
1H-benzo[f]chromene-2-carbonitrile (5i)
(43). HRMS (EI) Found: M+, 341.1502.
0.309g (90%); white solid; MP 156-158
C22H19N3O requires M+, 341.1505. Anal Calcd
o
C. IR (KBr): 3156, 3078, 2956, 2198, 1676,
for C22H19N3O: C, 77.40; H, 5.61; N, 12.31.
1534, 1412, 1123, 805 cm-1. 1H NMR (DMSO-
Found: C, 77.44; H, 5.64; N, 12.33.
d6, 500 MHz): 3.67 (s, 3H, OCH3), 5.32 (s,
1H, H-4), 5.53 (s, 1H, OH), 6.67 (s, 2H, NH2), 3-Amino-1-(naphthalen-2-yl)-1H-

7.16-7.31 (m, 4H, Ar-H), 7.32-7.45 (m, 2H, benzo[f]chromene-2-carbonitrile (5n)

13
Ar-H), 7.32-7.45 (m, 3H, Ar-H),. C NMR 0.320g (92%); white solid; mp 262-264
o
(DMSO-d6, 125 MHz): δ 39.53, 58.02, 59.43, C. IR (KBr): 3146, 3079, 2978, 2236, 1624,
120.93, 121.04, 122.54, 122.88, 124.43, 1545, 1434, 1121, 803 cm-1. 1H NMR (DMSO-
125.32, 125.92, 128.11, 129.98, 130.76, d6, 500 MHz): 5.28 (s, 1H, H-4), 6.57 (s, 2H,
131.73, 133.76, 134.08, 135.16, 142.05, NH2), 7.11-7.31 (m, 4H, Ar-H), 7.40-7.51 (m,
144.94, 147.74, 151.80, 157.43. MS (EI), m/z 3H, Ar-H), 7.53-7.72 (m, 3H, Ar-H), 7.81-8.06
(%) =344 (M+, 15), 221 (55). HRMS (EI) (m, 3H, Ar-H). 13
C NMR (DMSO-d6, 125
Found: M+, 344.1202. C21H16N2O3 requires MHz): δ 31.09, 65.54, 118.63, 120.87, 120.93,
+
M , 344.1209. Anal Calcd for C21H16N2O3: C, 122.09, 122.93, 125.02, 126.92, 128.54,
73.25; H, 4.67; N, 8.12. Found: C, 73.24; H, 130.08, 131.98, 132.98, 133.76, 136.98,
4.68; N, 8.13. 141.16, 145.05, 147.38, 149.94, 152.80,
3-Amino-1-(4-(dimethylamino)phenyl)-1H- 157.92, 161.98. MS (EI), m/z (%) =348 (M+,
benzo[f]chromene-2-carbonitrile (5k) 23), 221 (56). HRMS (EI) Found: M+,

Page | 77
 M.R. Poor Heravi, M. R. Amirloo / Iranian Chemical Communication 3 (2015) 73-84

348.1302. C24H16N2O requires M+, 348.1301. fect of water in these reactions is attributable
Anal Calcd for C24H16N2O: C, 82.74; H, 4.63; in part to its lubricating action, i.e., to its effect
N, 8.04. Found: C, 82.75; H, 4.64; N, 8.03. in reducing viscosity by decreasing the cou-
lombic interactions between cation and anion
Results and discussion
geater translation and rotational freedom. Fur-
In order to optimize the reaction condi-
thermore, the decreased hydrogen bonding
tions, we studied the synthesis of 4e and 5e
with anions [23, 24] should favor the catalytic
from the condensation of 1 or 2-naphthol, 4-
effect of IL, moreover, it is attributable to hy-
nitrobenzaldehyde and malononitrile in the
drogen-bonding between the imidazolium H-2
presence of a variety of solvents (Table 1, En-
atom and the carbonyl group of the aryalde-
tries 1-7). The successful results of experi-
hyde [25, 26]. Extra amount of [mim]Cl did
ments showed that the condensation reaction
not improve the yields (Table 1, Entries 12 and
without [mim]Cl in mixture of water and etha-
13). We also investigated the synthesis of our
nol (1:1) as polar and protic solvent is substan-
target compounds under solvent-free condi-
tially better than the corresponding reaction in
tions. The ionic liquid catalyst is in favor of
conventional organic solvents (Table 1, Entry
melting the reaction mixture and plays a cru-
7). We evaluated the amount of [mim]Cl re-
cial role in the success of the reaction in terms
quired for this transformation. It was found
of the rate and the yields. Reacting 4-
that when we increase the amount of IL from 1
nitrobenzaldehyde with (2) and (3) was ex-
to 20 mol%, the yields will increase from 40 to
amined as a reference. In accordance with Ta-
70% (Table 1, Entries 8-13). Using [mim]Cl
ble 1 and the general optimization procedure,
(10mol%) in water was sufficient to push the
10 mol% catalyst and 80 oC were used under
reaction forward (Table 1, Entry 10). The ef-
solvent-free conditions (Table 1, Entry 18).

Table 1. Optimization of conditions for synthesis of 2-amino-4-aryl-4H-benzo[h]chromene-3-carbonitrile

(4e) and 3-amino-1-aryl-1H-benzo[f]chromene-2-carbonitrile (5e) from 4-nitrobenzaldehydes (1e), malo-
nonitrile (2), and 1 or 2-naphthol (3) using [mim]Cl as catalyst under solvent-free conditions
Entry Catalyst (mol%) Solvent Temperature Time (h) Yield (%)a
(oC) 4e 5e
1 Non H2O 25 24 25 25
2 Non Ether 25 48 Nul Nul
3 Non CH2Cl2 25 24 5 5

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 One-pot multicomponent reaction for the synthesis of 2-amino-4-chromenes promoted by …

4 Non CH3Cl3 25 24 5 5
5 Non CH3CN 25 24 10 5
6 Non EtOH 25 20 30 25
7 Non H2O+ EtOH 25 20 35 35
8 1 H2O 25 20 40 40
9 5 H2O 25 20 55 50
10 10 H2O 25 20 75 70
11 15 H2O 25 20 75 70
12 20 H2O 25 20 75 70
13 25 H2O 25 20 70 70
14 Non Sovent-free 25 24 20 15
15 1 Sovent-free 50 0.8 76 65
16 5 Sovent-free 50 0.6 80 70
17 5 Sovent-free 80 0.5 83 75
18 10 Sovent-free 80 0.5 95 95
19 15 Sovent-free 80 0.5 95 95
20 20 Sovent-free 80 0.5 92 92
a
Isolated yields

The three-component, one-pot condensa- terms of reaction time under the reaction con-
tion of aldeh ydes, malononitrile and 1- ditions mentioned above. When aromatic alde-
naphthol or 2-naphthol proceeded in the pres- hydes containing electron-donating groups
ence of 10 mole% of [mim]Cl basic ionic liq- (such as hydroxyl, alkoxyl, or methyl group)
uids smoothly to give the corresponding prod- were employed (Table 2, Entries 8, 22, 12, 26,
ucts in high yields and the results are summa- 11 and 25), a longer reaction time was re-
rized in Table 2. quired than those of electron-withdrawing
groups (such as nitro group, halide) on aromat-
The scope and the generality of the
ic rings (Table 2, Entries 2–7 and 16-21 ). It is
present method were then demonstrated by the
worthy of note that the reaction proceeded
reaction of (1) with (2) and (3) (Scheme 1). In
without the protection of acidic hydroxyl subs-
all cases, good yields with good selectivity
tituent (Table 2, Entries 9, 23, 13 and 27).
were obtained. All of the results are shown in
Table 2. As can be seen from Table 2, elec-
tronic effects and the nature of substitute on
the aromatic ring did show strong effects in

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 M.R. Poor Heravi, M. R. Amirloo / Iranian Chemical Communication 3 (2015) 73-84

Table 2. Synthesis of 2-amino-4-aryl-4H-benzo[h]chromene-3-carbonitrile and 3-amino-1-aryl-1H-

benzo[f]chromene-2-carbonitrile using [mim]Cl as catalyst under solvent-free conditions
Naph- Prod-
Entry Ar Time/min Yields(/%)a Mp/C Lit. Mp/C
thol uct

1 C6H5 1 4a 40 92 209–211 210–211 [8]

2 4-ClC6H4 1 4b 30 93 231–232 231–232 [11]

3 2-ClC6H4 1 4c 40 70 237–238 236–237 [8]

4 2,4-Cl2C6H3 1 4d 35 82 220–222 222–224 [13]

5 4-NO2C6H4 1 4e 30 95 230–232 231–234 [11]

6 4-FC6H4 1 4f 30 98 228-230 229-231 [18]

7 4-CF3C6H4 1 4g 35 98 212-214 New Comp.

8 4-CH3OC6H4 1 4h 70 92 194–195 195-196 [11]

9 3-CH3O-4-OHC6H3 1 4i 75 90 136–138 137–139 [8]

10 3-NO2C6H4 1 4j 35 94 208–210 208–211 [11]

11 4-( CH3)2NC6H4 1 4k 60 85 201–203 203–205 [7]

12 4- CH3C6H4 1 4l 50 90 205–206 205–206 [14]

13 4-HOC6H4 1 4m 50 88 244–246 245-247 [15]

14 2-Naphthyl 1 4n 45 92 256-257 New Comp.

15 C6H5 2 5a 60 92 279–280 278–280 [19]

16 4-ClC6H4 2 5b 75 93 209–210 208–210 [19]

17 2-ClC6H4 2 5c 80 70 237–238 274–276 [20]

18 2,4-Cl2C6H3 2 5d 60 82 220–222 219–222 [22]

19 4-NO2C6H4 2 5e 50 95 230–232 188–189 [21]

20 4-FC6H4 2 5f 55 98 231-232 232-233 [6]

21 4-CF3C6H4 2 5g 55 98 235-237 New Comp.

22 4-CH3OC6H4 2 5h 85 92 190–192 191-193 [6]

23 3-CH3O-4-OHC6H3 2 5i 90 90 156–158 New Comp.

24 3-NO2C6H4 2 5j 50 94 211–213 210–212 [18]

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 One-pot multicomponent reaction for the synthesis of 2-amino-4-chromenes promoted by …

25 4-(CH3)2NC6H4 2 5k 95 85 251–253 New Comp.

26 4- CH3C6H4 2 5l 75 90 205–206 270–272 [22]

27 4-HOC6H4 1 5m 50 85 234–236 235-237 [15]

28 2-Naphthyl 2 5n 60 92 262-264 New Comp.

a
Isolated yield

The mechanism proposed for preparation of 2-amino-4-aryl-4H-benzo[h]chromene-3-

carbonitrile and 3-amino-1-aryl-1H- lyst, ortho C-alkylation of the electrophilic

benzo[f]chromene-2-carbonitrile from arylal- C=C double bond by 1 or 2-naphthol then
dehydes, malononitrile, and 1 or 2-naphthol gives intermediates (I). Tautomerization con-
using [mim]Cl as catalyst under solvent-free verts intermediate (I) to intermediate (II),
conditions is depicted in Scheme 2. According which is then cyclized by nucleophilic attack
to the literature [6], arylidene malononitrile, of an OH group on the China (CN) moiety to
containing an electron-poor C=C double bond, give intermediate (III). Subsequently, tautome-
is formed quantitatively by the Knoevenagel rization produced the 2-amino-4-aryl-4H-
addition of malononitrile to the aromatic alde- benzo[h]chromene-3-carbonitrile (4a-n).
hyde in the presence of ionic liquids as cata-

Scheme 2. Proposed mechanisms for preparation of 2-amino-4-chromenes promoted by [mim]Cl ionic-

liquid catalyst under solvent-free conditions

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 M.R. Poor Heravi, M. R. Amirloo / Iranian Chemical Communication 3 (2015) 73-84

In view of the green chemistry, the cata- turn after evaporation of water under reduced
lyst was further explored for the reusability by pressure. The recycled catalyst has been
a model reaction of 4-nitrobenzaldehyde and reused five times to catalyze the model reac-
reactants 2 and 3 (1 or 2-naphtol) under similar tion affording the corresponding chromene in
conditions in the presence of 10 mole% cata- 92, 91, 90, 89, and 87% yields, and without
lyst. The catalyst was easily recovered by appreciable decreases of yield.
washing the reaction mixture with distilled wa-
ter and then was directly reused for the next

Figure 1. Reusability of [mim]Cl ionic-liquid catalyst. Reaction of 4-nitrobenzaldehyde, malononitrile, and 1-

naphthol or 2-naphthol was used as model reaction

In conclusion, we describe a practical and periment and isolated procedure made it a use-
efficient procedure for the preparation of 2- ful and attractive protocol for the synthesis of
amino-4-criminals through the three- these compounds. The catalyst was reused by
component reaction of aromatic aldehydes another cycle after evaporation of water. All of
(1a-n), malononitrile (2), and 1-naphthol (3) the products are known and the data are found
using a catalytic amount of [mim]Cl catalyst to be identical with those that reported in the
under solvent-free conditions. This procedure literature (Table 2).
offers several advantages, including mild reac-
Conclusion
tion conditions, cleaner reaction, and satisfac-
In this research, mild ionic liquid [mim]Cl
tory yields of products, as well as a simple ex-
was used as catalysts, for the first time, for

Page | 82
preparation of 2-amino-4-aryl-4H- [4] E. A. A. Hafez, M. H. Elnagdi, A. G. A.
benzo[h]chromene-3-carbonitrile and 3-amino- Elagamey, F. M. A. Ei-Taweel, Heterocycles
1-aryl-1H-benzo[f]chromene-2-carbonitrile 1987, 26, 903-907.
under solvent-free conditions at 80 C. The
[5] A. G. A. Elagamey, F. M. A. El-Taweel,
attractive features of this method are the sim-
Indian J. Chem. B 29B,1990, 885-886.
ple procedure, cleaner reaction, and use of in-
expensive and reusable ionic liquid as a cata- [6] R. Ballini, G. Bosica, M. L. Conforti, R.
lyst under solvent-free conditions. Satisfactory Maggi, A. Mazzacanni, P. Righi, G. Sartori,
yields and simple isolation and purification of Tetrahedron, 2001, 57, 1395-1402.
the products make it a useful procedure for
synthesis of these compounds. [7] T. S. Jin, J. C. Xiao, S. J. Wang, T. S. Li,
X. R. Song, Syn lett, 2003, 2001-2004.
Acknowledgments

We are grateful to the Payame Noor Uni- [8] T. S. Jin, J.C. Xiao, S. J. Wang, T. S. Li,
versity of Tehran for the support of this study. Ultrason. Sonochem., 2004, 11, 393-397.

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