Protic pyridinium ionic liquid: As an efficient, green and environmentally friendly catalyst for the one-pot synthesis of amidoalkyl naphthol derivatives

Article abstract of DOI:10.1016/j.crci.2012.10.012

A green and efficient synthesis of amidoalkyl naphthol derivatives via the three-component reaction between aryl aldehyde, 2-naphthol and amide derivatives using 2-methylpyridinium trifluoromethanesulfonate ([2-MPyH]OTf) as a catalyst (5 mol%) is describe

Full text of DOI:10.1016/j.crci.2012.10.012

G Model
CRAS2C-3638; No. of Pages 5
C. R. Chimie xxx (2013) xxx–xxx
Contents lists available at SciVerse ScienceDirect
Comptes Rendus Chimie
www.sciencedirect.com
´
Full paper/Memoire
Protic pyridinium ionic liquid: As an efficient, green and environmentally
friendly catalyst for the one-pot synthesis of amidoalkyl naphthol
derivatives
c
Heshmatollah Alinezhad a, Mahmood Tajbakhsh a, Mohammad Norouzi a,b, , Saeed Baghery ,
*
Maryam Akbari b
a Department of Chemistry, Mazandaran University, Babolsar, Iran
b Department of Chemistry, Payame Noor University, P.O. Box 19395-3697, Tehran, Iran
c Young Researchers Club, Ayatollah Amoli Branch, Islamic Azad University, Amol, Iran
A R T I C L E I N F O
A B S T R A C T
Article history:
A green and efficient synthesis of amidoalkyl naphthol derivatives via the three-
component reaction between aryl aldehyde, 2-naphthol and amide derivatives using 2-
methylpyridinium trifluoromethanesulfonate ([2-MPyH]OTf) as a catalyst (5 mol%) is
described. This method provides several advantages over alternative procedures such as
low cost, under thermal solvent-free green procedure, simple procedure and direct
isolation of the products in high yields.
Received 17 August 2012
Accepted after revision 22 October 2012
Available online xxx
Keywords:
Amidoalkyl naphthol
2-Methylpyridinium
trifluoromethanesulfonate
Ionic liquid
´
ß 2012 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.
One-pot synthesis
Solvent-free condition
1. Introduction
probes and ionic channel blockers [9], phase-transfer
catalysts [10] and IL crystal applications [11–13].
Ionic liquids have received widespread attention as
mediums for a variety of reactions because of their
properties such as very low or practically no vapor
pressure, remarkable solubility behavior and the possibil-
ity of varying their structure to manipulate parameters like
density, solubility and reusable ‘green’ solvent for chemi-
cal reactions [1–3]. Ionic liquids (ILs) or room-temperature
molten salts have attracted much attention from chemists
in recent years [4–7]. Representing a new class of non-
molecular ionic compounds, ionic liquids were extensively
investigated as reaction media (solvents) [8], molecular
Multi-component reactions (MCRs) have attracted
considerable attention since an increasing number of
organic chemical compounds are formed by multi-
component reactions (MCRs) that convert more than
two educts directly into their products by one-pot
reactions. Further, they are performed without need to
isolate any intermediate during their processes; this
reduces time and saves both energy and raw material.
They have merits over two-component reactions in several
aspects including the simplicity of a one-pot procedure,
possible structural variations and building up complex
molecules [14]. One of these MCRs is the preparation of
amidoalkyl naphthols. It is worthy to note that by amide
hydrolysis reaction, 1-amidomethyl-2-naphthols can be
converted to important biologically active 1-amino-
methyl-2-naphthol derivatives. The hypotensive and
bradycardiac effects of these compounds have been
reported [15]. The preparation of amidoalkyl naphthols
* Corresponding author. Present address: department of Chemistry,
Payame Noor University, P.O. Box 19395-3697, Tehran, Iran.
E-mail addresses: mnorouzi346@yahoo.com, mnorouzi346@pnu.ac.ir
(M. Norouzi).
1631-0748/$ – see front matter ß 2012 Acade´mie des sciences. Published by Elsevier Masson SAS. All rights reserved.
http://dx.doi.org/10.1016/j.crci.2012.10.012
Please cite this article in press as: Alinezhad H, et al. Protic pyridinium ionic liquid: As an efficient, green and
environmentally friendly catalyst for the one-pot synthesis of amidoalkyl naphthol derivatives. C. R. Chimie (2013),
http://dx.doi.org/10.1016/j.crci.2012.10.012

G Model
CRAS2C-3638; No. of Pages 5
2
H. Alinezhad et al. / C. R. Chimie xxx (2013) xxx–xxx
OH
O
O
[2-MPyH]OTf (5 mol%)
Solvent-free, 125 oC
OH
O
+
+
R
NH2
Ar
H
Ar
NH
1
2
3
R: NH2, CH3, Ph
4
R
F
F
O
NH+
S
Catalyst: [2MPyH]OTf
-
F
O
O
Scheme 1. A simple green procedure for the synthesis of amidoalkyl naphthol using [2-MPyH]OTf.
can be carried out by multi-component condensation of
aryl aldehydes, 2-naphthol and acetonitrile or amide in the
presence of Lewis or Brønsted acid catalysts such as
HClO4–SiO2 [16], heteropolyacids [17,18], montmorillon-
ite K10 clay [19], P2O5 [20], sulfamic acid [21], Brønsted
acidic ionic liquid [22], cyanuric chloride [23], Sodium
hydrogen sulfate [24], Ce(SO4)2 [25] and Sr(OTf)2 [26].
However, some of these methods are associated with
prolonged reaction time, toxicity and low yields of desired
product. Further, when a solid aldehyde or high amounts of
catalyst is used, an organic solvent such as dichloroethane
is needed [21].
continuation of our previous works on the application of
reusable acidic ionic liquid in organic synthesis we decided
to investigate the synthesis of amidoalkyl naphthol
derivatives in the presence of 2-methylpyridinium tri-
fluoromethanesulfonate ([2-MPyH]OTf) [28] as a green
and highly efficient catalyst.
2. Results and discussion
In the present study, we describe a simple and green
procedure for the preparation of amidoalkyl naphthol
derivatives (4) via
a three-component condensation
In this article, there is growing interest in development
of clean processes involving green catalysts. In recent
years, ionic liquids have attracted much attention as a new
class of green solvents and catalyst [27]. Thus, in
reaction between aryl aldehydes (1), 2-naphthol (2) and
amide (3) in the presence of [2-MPyH]OTf as a heteroge-
neous catalyst under thermal solvent-free conditions
(Scheme 1).
Table 1
Synthesis of amidoalkyl naphthol derivatives catalyzed by [2-MPyH]OTf under thermal solvent-freea.
Entry
Aryl aldehyde
R
M.p (8C)
Time (min)
Yield (%)b [Reference]
1
Benzaldehyde
NH2
NH2
NH2
NH2
NH2
NH2
NH2
NH2
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
Ph
173–175
149–151
169–171
141–143
168–170
241–243
185–187
164–166
228–230
195–197
236–238
225–227
231–233
203–205
164–166
252–254
193–195
202–204
225–227
82–84
30
20
15
15
20
20
10
15
45
35
30
30
30
35
30
35
45
45
30
20
30
30
20
35
20
30
35
30
20
15
92 [21]
94 [17]
95 [21]
95 [17]
94 [21]
93 [18]
97 [21]
95 [17]
91 [21]
92 [21]
94 [20]
93 [19]
93 [22]
92 [23]
93 [20]
92 [16]
91 [19]
93 [24]
94 [20]
96 [25]
94 [25]
94 [21]
96 [20]
91 [21]
95 [21]
93 [19]
91 [19]
94 [21]
96 [21]
96 [26]
2
2-Chlorobenzaldehyde
4-Chlorobenzaldehyde
2,4-Dichlorobenzaldehyde
4-Bromobenzaldehyde
3-Methoxybenzaldehyde
3-Nitrobenzaldehyde
1-Naphthaldehyde
3
4
5
6
7
8
9
Benzaldehyde
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
2-Chlorobenzaldehyde
4-Chlorobenzaldehyde
2,4-Dichlorobenzaldehyde
4-Bromobenzaldehyde
3-Methoxybenzaldehyde
4-Methoxybenzaldehyde
2,5-Dimethoxybenzaldehyde
3,4,5-Trimethylbenzaldehyde
2-Methylbenzaldehyde
4-Methylbenzaldehyde
4-Dimethylaminobenzaldehyde
2-Nitrobenzaldehyde
3-Nitrobenzaldehyde
4-Nitrobenzaldehyde
Benzaldehyde
181–183
241–243
236–238
234–236
174–176
168–170
237–239
191–193
216–218
244–246
4-Chlorobenzaldehyde
3-Methoxybenzaldehyde
3,4,5-Trimethylbenzaldehyde
4-Methylbenzaldehyde
3-Nitrobenzaldehyde
4-Nitrobenzaldehyde
Ph
Ph
Ph
Ph
Ph
Ph
a
Aryl aldehyde (1 mmol), 2-naphthol (1 mmol), amide derivatives (1.2 mmol), [2-MPyH]OTf as a catalyst (5 mol%).
Isolated yield.
b
Please cite this article in press as: Alinezhad H, et al. Protic pyridinium ionic liquid: As an efficient, green and
environmentally friendly catalyst for the one-pot synthesis of amidoalkyl naphthol derivatives. C. R. Chimie (2013),
http://dx.doi.org/10.1016/j.crci.2012.10.012

G Model
CRAS2C-3638; No. of Pages 5
H. Alinezhad et al. / C. R. Chimie xxx (2013) xxx–xxx
3
Table 2
Table 3
Optimization of the amount of [2-MPyH]OTf and the reaction tempera-
ture for the preparation of N-((2-hydroxynaphthalen-1-yl)(phenyl)-
methyl)acetamide (Table 1 entry 9)a.
Reusability studies of catalysts for the synthesis of N-((2-hydroxy-
naphthalen-1-yl)(phenyl)methyl)acetamide (Table 1 entry 9)a.
Catalytic run
Fresh
91
1
2
3
4
Entry
Catalyst
Temperature
Time
Yield (%)b
Isolated yield (%)b
91
90
89
89
amount (mol%)
(8C)
(min)
a
Benzaldehyde (1 mmol), 2-naphthol (1 mmol), acetamide (1.2 mmol),
[2-MPyH]OTf as a catalyst (5 mol%).
1
2
3
4
5
6
1
5
125
100
125
100
125
125
180
90
45
90
45
45
60
85
91
85
91
91
b
Isolated yield.
5
10
10
15
acetamide was found to be advantageous and hence the
molar ratio of 2-naphthol to acetamide was kept at 1:1.2.
To optimize the temperature in the mentioned reaction,
we have carried out a model study with benzaldehyde and
2-naphthol and acetamide using 5 mol% of catalyst at
various temperatures under solvent-free conditions. Table
a
Benzaldehyde (1 mmol), 2-naphthol (1 mmol), acetamide (1.2 mmol).
Isolated yield.
b
To study the generality of this process, several examples
illustrating this method for the synthesis those amidoalkyl
naphthol derivatives were studied. To show the general
applicability of this method, various aryl aldehydes were
efficiently reacted with 2-naphthol and amide derivatives
in the same conditions. The results are summarized in
Table 1. The effect of electron and the nature of
substituents on the aromatic ring did show expected
strong effects in terms of yields under these reaction
conditions. Aromatic aldehydes containing electron-with-
drawing groups (such as nitro groups) or electron-
donating groups (such as methoxy groups) were employed
and they were found to react well to give the correspond-
ing amidoalkyl naphthol in good to excellent yields.
Aromatic aldehydes having electron-withdrawing groups
on the aromatic ring (Table 1, entries 7, 21, 22, 23 29, 30)
react faster than electron-donating groups (Table 1, entries
6, 14, 15, 26).
2 clearly demonstrates that 125 8C is an effective
temperature in terms of reaction time and yield obtained.
The reusability of the catalysts is an important
advantage and makes them useful for commercial
applications. The catalyst plays a crucial role in the success
of the reaction in terms of the rate and the yields [29]. For
example, benzaldehyde reacted with 2-naphthol and
acetamide in the presence of 5 mol% ionic liquid catalyst
to give the N-((2-hydroxynaphthalen-1-yl)(phenyl)-
methyl)acetamide in 91% yield under thermal solvent-
free conditions after 45 min of reaction time. After
completion of the reaction (monitored by TLC), the product
was extracted with CH2Cl2 and the catalyst was recovered
from the aqueous layer. Ionic liquid catalyst is more
soluble in water than in CH2Cl2 solvent. The catalyst could
be reused five times for the synthesis of analogues product
without significant loss of activity. The results were
summarized in Table 3.
To find out the optimum quantity of [2-MPyH]OTf, the
reaction of 2-naphthol, benzaldehyde, and acetamide was
carried out under thermal solvent-free conditions using
different quantities of [2-MPyH]OTf (Table 2). Ionic liquid
[2-MPyH]OTf as a catalyst of 5 mol% gave excellent yield in
45 min as can be seen from Table 2. A slight excess of the
In Scheme 2, we propose a possible mechanism for the
synthesis of amidoalkyl naphthol derivatives in the
presence of [2-MPyH]OTf as a catalyst. The reaction of
2-naphthol with aromatic aldehydes in the presence of
ionic liquid as a catalyst is known to give ortho-quinone
N+
-
Ar
H
CF3SO3
H
H
-
N
O
CF3SO3
O
H O
-
H+
O
2
Ar
H
Ar
1
OH
o-QMs
2
O
Ar
NHCOR
OH
Ar
H
-
N
OH+
R
NH2
CF3SO3
H+
3
4
Scheme 2. Suggested mechanism for the synthesis of amidoalkyl naphthols via conjugate addition reaction.
Please cite this article in press as: Alinezhad H, et al. Protic pyridinium ionic liquid: As an efficient, green and
environmentally friendly catalyst for the one-pot synthesis of amidoalkyl naphthol derivatives. C. R. Chimie (2013),
http://dx.doi.org/10.1016/j.crci.2012.10.012

G Model
CRAS2C-3638; No. of Pages 5
4
H. Alinezhad et al. / C. R. Chimie xxx (2013) xxx–xxx
methides (o-QMs). The same o-QMs, generated in situ,
have been reacted with amide to form amidoalkyl
naphthol derivatives. A reasonable explanation for this
result can be given by considering the nucleophilic
addition to o-QMs intermediate favorable via conjugate
addition on the a,b-unsaturated carbonyl group and finally
this intermediate will aromatize to produce the final
aromatic compound [30].
4.3. Recycling of [2-MPyH]OTf as an ionic liquid catalyst
In case of a hydrophilic ionic liquid, i.e., [2-MPyH]OTf,
the reaction mixture was diluted water and extracted with
CH2Cl2 (2 * 10 mL). The combined organic extracts were
washed with water, dried over anhydrous Na2SO4,
concentrated under vacuum and the resulting product
was purified either by recrystallization to afford pure
product. The ionic liquid can be recovered either by
extracting the aqueous phase with CH2Cl2 or by evaporat-
ing the aqueous layer under vacuum. The ionic liquid thus
obtained was further dried at 60 8C under reduced pressure
for use in subsequent runs.
3. Conclusion
In summary, this article describes a green, simple and
efficient protocol for the synthesis of amidoalkyl naphthol
derivatives by the reaction of between aldehyde, 2-naphtol
and amide in the presence of [2-MPyH]OTf. The notable
merits of this protocol are cleaner reaction conditions,
shorter time reaction, improved yields and simple
experimental and work-up procedure. Also, the catalysts
were able to be reused easily for five-time experiments
with a small decrease in the catalytic activity of the
recovered catalyst.
4.4. Spectral data for the synthesis of amidoalkyl naphthol
derivatives
4.4.1. 1-((2-hydroxynaphthalen-1-yl)(3-
methoxyphenyl)methyl)urea (Table 1, entry 6)
Yield: 93%; M.p 241-243 8C (lit. [18] 242–244 8C); IR
(KBr, cmÀ1) 3485, 3407, 3371, 3175, 3067, 2957, 1649,
1601, 1527, 1435, 1067, 825, 739; 1H NMR (400 MHz,
˙
˙
4. Experimental
CDCl3): d 3 63 (s, 3H), 5 87 (s, 2H), 7.17 (d, J = 8.5 Hz, 1H),
7.21 (t, J = 8.1 Hz, 1H), 7.27 (t, J = 7.6 Hz, 1H), 7.41 (t,
J = 7.5 Hz, 1H), 7.53 (m, 2H), 7.77 (t, J = 8.5 Hz, 2H), 7.86
All starting materials were obtained from Merck and
Fluka, and were used without further purification. Melting
points were obtained on a Thermo Scientific apparatus and
were not corrected. IR spectra were recorded on a FT-IR
Bruker (WQF-510) spectrometer. 1H and 13C NMR spectra
were recorded on a Bruker DRX-400 AVANCE spectrometer
(400 and 100 MHz, respectively). Mass spectra were
recorded on an Agilent technologies 5973 network mass
selective detector (MSD) operating at an ionization
potential of 70 eV.
˙
(brs, 1H), 7.97 (m, 2H), 8.59 (d, J = 8.1 Hz, 1H), 9 96 (s, 1H);
13C NMR (100 MHz, CDCl3):
27.3, 48.5, 118.7, 119.1,
d
120.7, 121.5, 123.6, 127.1, 123.5, 128.7, 129.1, 130.1, 130.9,
132.4, 133.7, 145.8, 148.1, 153.7, 170.1; MS m/z = 322 (M+,
7.11%), 320 (30.27%), 276 (37.49%), 260 (65.01%), 230
(100%), 202 (55.17%), 189 (8.09%), 144 (33.58%), 127
(19.29%), 115 (36.67%), 101 (27.51%), 88 (15.87%), 77
(17.21%), 63 (12.11%), 51 (13.51%).
4.4.2. 1-((2-hydroxynaphthalen-1-yl)(3-
4.1. General procedure for the synthesis of ionic liquid
catalyst
nitrophenyl)methyl)urea (Table 1, entry 7)
Yield: 97%; M.p 185-187 8C (lit. [21] 184–186 8C); IR
(KBr, cmÀ1) 3415, 3390, 3357, 3130, 2977, 1651, 1600,
1545, 1437, 1375, 1060, 957, 741; 1H NMR (400 MHz,
The ionic liquid [2-MPyH]OTf as
a catalyst was
˙
synthesized according to literature [28]. A white solid
was formed in high purity and then the physical data (IR,
NMR) of these known ionic liquid was found to be
identical. Spectral data: IR (KBr, cmÀ1) 2983, 1631, 1365,
CDCl3): d 5 97 (s, 2H), 7.18 (t, J = 8.1 Hz, 1H), 7.23 (d,
J = 8.5 Hz, 1H), 7.28 (t, J = 7.7 Hz, 1H), 7.39 (t, J = 7.3 Hz, 1H),
7.57 (m, 2H), 7.71 (t, J = 8.5 Hz, 2H), 7.87 (brs, 1H), 7.97 (m,
2H), 8.61 (d, J = 8.2 Hz, 1H), 10 17 (s, 1H); 13C NMR
˙
1223, 1070, 957, 887, 579; 1H NMR (400 MHz, CDCl3):
d
(100 MHz, CDCl3): d 47.9, 117.8, 118.7, 120.8, 121.3, 122.7,
2.93 (s, 3H), 7.26–7.67 (m, 2H), 8.29–8.36 (m, 1H), 8.84 (d,
126.9, 128.5, 129.7, 131.1, 132.3, 133.9, 145.7, 147.9, 154.5,
170.7; MS m/z = 337 (M+, 7.28%), 336 (28.49%), 276
(18.37%), 260 (70.21%), 230 (100%), 202 (28.09%), 189
(6.51%), 145 (6.67%), 115 (12.83%), 43 (23.27%).
J = 5.9 Hz, 1H), 17.21 (brs, 1H); 13C NMR (100 MHz, CDCl3):
d
154.1, 146.7, 141.3, 128.1, 125.3, 120.7, 21.1.
4.2. General procedure for the synthesis of amidoalkyl
naphthol derivatives
4.4.3. N-((2-hydroxynaphthalen-1-
yl)(phenyl)methyl)acetamide (Table 1, entry 9)
Yield: 91%; M.p 228-230 8C (lit. [21] 229–230 8C); IR
(KBr, cmÀ1) 3397, 3241, 3057, 2955, 1637, 1580, 1375,
To
a mixture of aldehydes (1 mmol), 2-naphthol
(1 mmol) and acetamide (1.2 mmol), effective amount of
ionic liquid [2-MPyH]OTf as a catalyst was added. The
mixture was stirred under thermal solvent-free condition
at 125 8C in oil bath for appropriate time and the reaction
was followed by TLC. After completion of reaction, mass
was cooled to room temperature, then the solid residue
was dissolved in ethyl acetate and the mixture stirred for
5 min. Then solvent was evaporated, the remaining solid
product was recrystallized in aqueous ethanol-water.
1337, 1057, 898, 745; 1H NMR (400 MHz, CDCl3):
d 1.97 (s,
3H), 7.09 (m, 1H), 7.13 (m, 1H), 7.17 (m, 1H), 7.21 (m, 1H),
7.20 (m, 2H), 7.23 (m, 1H), 7.27 (m, 1H), 7.35 (t, J = 7.6 Hz,
1H), 7.74 (d, J = 9.3 Hz, 1H), 7.79 (d, J = 7.9 Hz, 1H), 7.87 (s,
1H), 8.46 (d, J = 8.6 Hz, 1H), 10.03 (s, 1H); 13C NMR
(100 MHz, CDCl3):
d 23.1, 40.3, 119.3, 119.7, 123.1, 123.8,
126.4, 126.8, 127.5, 128.3, 128.9, 129.2, 129.7, 131.9, 143.2,
155.7, 169.3; MS m/z = 305 (M+, 21%), 246 (29.16%), 245
Please cite this article in press as: Alinezhad H, et al. Protic pyridinium ionic liquid: As an efficient, green and
environmentally friendly catalyst for the one-pot synthesis of amidoalkyl naphthol derivatives. C. R. Chimie (2013),
http://dx.doi.org/10.1016/j.crci.2012.10.012

G Model
CRAS2C-3638; No. of Pages 5
H. Alinezhad et al. / C. R. Chimie xxx (2013) xxx–xxx
5
(50.57%), 231 (100%), 232 (31.18%), 202 (16.11%), 115
(10.05%).
z = 398 (M+, 12.27%), 381 (49.51%), 276 (26.87%), 260
(34.71%), 246 (6.53%), 230 (52.67%), 202 (24.03%), 115
(11.31%), 105 (100%), 77 (54.17%), 51 (7.57%).
4.4.4. N-((2-hydroxynaphthalen-1-yl)(3-
methoxyphenyl)methyl)acetamide (Table 1, entry 14)
Yield: 92%; M.p 203-205 8C (lit. [23] 202–204 8C); IR
(KBr, cmÀ1) 3395, 3261, 2957, 1657, 1605, 1545, 1437,
Acknowledgement
1065, 879, 739; 1H NMR (400 MHz, CDCl3):
d 2.01 (s, 3H),
This research was supported by the make inquiries
commission of the University of Payame Noor, Sari, Iran.
3.65 (s, 3H), 7.15 (t, J = 8.1 Hz, 1H), 7.17 (d, J = 8.5 Hz, 1H),
7.23 (t, J = 7.6 Hz, 1H), 7.36 (t, J = 7.5 Hz, 1H), 7.52 (m, 2H),
7.75 (t, J = 8.5 Hz, 2H), 7.81 (brs, 1H), 7.97 (m, 2H), 8.59 (d,
References
J = 8.1 Hz, 1H), 10.15 (s, 1H); 13C NMR (100 MHz, CDCl3):
d
[1] Y.Y. Jiang, G.N. Wang, Z. Zhou, Y.T. Wu, J. Geng, Z.B. Zhang, Chem.
Commun. (2008) 505.
[2] D. Kuang, S. Uchida, R. Humphry-Baker, S.M. Zakeeruddin, M. Graetzel,
Angew. Chem. Int. Ed. 47 (2008) 1923.
[3] T. Singh, A. Kumar, J. Phys. Chem. B 112 (2008) 4079.
[4] D.M. Eike, J.F. Brennecke, E.J. Maginn, Green Chem. 5 (2003) 323.
[5] E.R. Cooper, C.D. Andrews, P.S. Wheatley, P.B. Webb, P. Wormald, R.E.
Morris, Nature 430 (2004) 1012.
23.3, 33.5, 48.9, 118.7, 119.1, 120.7, 121.9, 123.3, 123.9,
127.2, 128.7, 129.1, 130.2, 130.9, 132.4, 133.5, 145.7, 148.1,
153.8, 169.5; MS m/z = 322 (M+, 8.01%), 321 (32.23%), 278
(5.01%), 261 (49.18%), 247 (15.32%), 231 (100%), 218
(12.07%), 202 (7.25%), 189 (9.38%), 134 (9.31%) 115
(11.17%), 109 (4.03%) 43 (14.06%).
[6] T. Welton, Chem. Rev. 99 (1999) 2071.
[7] J. Dupont, G.S. Fonseca, A.P. Umpierre, P.F.P. Fichtner, S.R. Teixeira, J.
Am. Chem. Soc. 124 (2002) 4228.
4.4.5. N-((2-hydroxynaphthalen-1-yl)(4-
[8] M. Picquet, D. Poinsot, S. Stutzmann, I. Tkatchenko, I. Tommasi, P.
Wasserscheid, J. Zimmermann, Top. Catal. 29 (2004) 139.
[9] V.B. Luzhkov, F. Ssterberg, P. Acharya, J. Chattopadhyaya, J. Tqvist, Phys.
Chem. Chem. Phys. 4 (2002) 4640.
[10] D.X. Xu,S.P. Luo,B.Y. Liu,X.H. Yan,Z.Y.Xu,Chin.J.Org. Chem.24(2002)99.
[11] K. Binnemans, Chem. Rev. 105 (2005) 4148.
[12] J. Kadam, C.F.J. Faul, U. Scherf, Chem. Mater. 16 (2004) 3867.
[13] D.J. Abdallah, A. Robertson, H. Hsu, R.G. Weiss, J. Am. Chem. Soc. 122
(2000) 3053.
[14] D. Dallinger, A. Stadler, C.O. Kappe, Pure Appl. Chem. 76 (2004) 1017.
[15] A.Y. Shen, C.T. Tsai, C.L. Chen, Eur. J. Med. Chem. 34 (1999) 877.
[16] H.R. Shaterian, H. Yarahmadi, M. Ghashang, Tetrahedron 64 (2008)
1263.
[17] L. Nagarapu, M. Baseeruddin, S. Apuri, S. Kantevari, Catal. Commun. 8
(2007) 1729.
nitrophenyl)methyl)acetamide (Table 1, entry 23)
Yield: 96%; M.p 236-238 8C (lit. [20] 237–238 8C); IR
(KBr, cmÀ1) 3397, 3265, 2978, 2573, 1647, 1615, 1535,
1437, 1357, 1063, 877, 739; 1H NMR (400 MHz, CDCl3):
d
2.03 (s, 3H), 7.21 (d, J = 8.1 Hz, 1H), 7.25 (d, J = 8.7 Hz, 1H),
7.29 (t, J = 7.7 Hz, 1H), 7.43 (t, J = 7.5 Hz, 1H), 7.53-7.59 (m,
2H), 7.83 (t, J = 9.3 Hz, 2H), 7.89 (d, J = 7.2 Hz, 1H), 8.07 (m,
2H), 8.63 (d, J = 8.1 Hz, 1H), 10.13 (s, 1H); 13C NMR
(100 MHz, CDCl3):
d 22.7, 47.9, 117.9, 118.5, 120.8, 121.4,
122.7, 126.9, 128.7, 129.5, 130.1, 132.3, 133.9, 146.1, 147.9,
153.3, 170.1; MS m/z = 336 (M+, 26.67%), 319 (75.97%), 276
(52.03%), 260 (54.11%), 231 (63.83%), 202 (45.13%), 230
(100%), 115 (18.02%).
[18] A.R. Supale, G.S. Gokavi, J. Chem. Sci. 122 (2010) 189.
[19] S. Kantevari, S.V.N. Vuppalapati, L. Nagarapu, Catal. Commun. 8 (2007)
1857.
[20] G.C. Nandi, S. Samai, R. Kumar, M.S. Singh, Tetrahedron Lett. 50 (2009)
7220.
4.4.6. N-((2-hydroxynaphthalen-1-yl)(3-
nitrophenyl)methyl)benzamide (Table 1, entry 29)
Yield: 96%; M.p 216-218 8C (lit. [21] 214–216 8C); IR
(KBr, cmÀ1) 3395, 3267, 2975, 1657, 1615, 1535, 1460,
[21] S.B. Patil, P.R. Singh, M.P. Surpur, S.D. Samant, Ultrason. Sonochem. 14
(2007) 515.
[22] A.R. Hajipour, Y. Ghayeb, N. Sheikhan, A.E. Ruoho, Tetrahedron Lett. 50
(2009) 5649.
1075, 957, 748; 1H NMR (400 MHz, CDCl3):
d 7.15 (t,
[23] G.H. Mahdavinia, M.A. Bigdeli, Chin. Chem. Lett. 20 (2009) 383.
[24] H.R. Shaterian, H. Yarahmadi, Arkivoc 2 (2008) 105.
[25] N.P. Selvam, P.T. Perumal, Tetrahedron. Lett. 47 (2006) 7481.
[26] W.K. Su, W.Y. Tang, J. Li, J. Chem. Res. (2008) 123.
[27] A. Khalafi-Nezhad, B. Mokhtari, Tetrahedron Lett. 45 (2004) 6737.
[28] Z. Duan, Y. Gu, J. Zhang, L. Zhu, Y. Deng, J. Mol. Catal. A: Chem. 250
(2006) 163.
[29] T.S. Jin, J.S. Zhang, T.T. Guo, A.Q. Wang, T.S. Li, Synthesis (2004) 2001.
[30] B. Das, K. Laxminarayana, B. Ravikanth, B.R. Rao, J. Mol. Catal. A: Chem.
261 (2007) 180.
J = 8.3 Hz, 1H), 7.18 (d, J = 8.3 Hz, 1H), 7.23 (t, J = 7.3 Hz, 1H),
7.41 (t, J = 7.5 Hz, 1H), 7.54 (m, 2H), 7.69 (d, J = 8.2 Hz, 2H),
7.74 (t, J = 8.5 Hz, 2H), 7.89 (m, 1H), 7.97 (m, 2H), 8.07 (d,
˙
˙
J = 8.2 Hz, 2H), 8.61 (d, J = 8.1 Hz, 1H), 9 17 (brs, 1H), 10 43
(s, 1H); 13C NMR (100 MHz, CDCl3):
47.7, 117.9, 118.7,
d
120.5, 121.3, 122.7, 126.5, 127.8, 128.4, 128.7, 129.3, 129.7,
132.3, 132.8, 133.5, 145.4, 147.6, 153.8, 169.7; MS m/
Please cite this article in press as: Alinezhad H, et al. Protic pyridinium ionic liquid: As an efficient, green and
environmentally friendly catalyst for the one-pot synthesis of amidoalkyl naphthol derivatives. C. R. Chimie (2013),
http://dx.doi.org/10.1016/j.crci.2012.10.012