Design of 1-methylimidazolium tricyanomethanide as the first nanostructured molten salt and its catalytic application in the condensation reaction of various aromatic aldehydes, amides and β-naphthol compared with tin dioxide nanoparticles

Article abstract of DOI:10.1039/c5ra02718g

1-Methylimidazolium tricyanomethanide {[HMIM]C(CN)₃} as a novel, green and nano molten salt catalyst was designed and fully identified by IR, ¹H NMR, ¹³C NMR, mass, thermal gravimetric (TG), derivative thermal gravimetric

Full text of DOI:10.1039/c5ra02718g

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ARTICLE TYPE
Design of 1-methylimidazolium tricyanomethanide as the first
nanostructured molten salt and its catalytic application on the
condensation reaction of various aromatic aldehydes, amide and β-
naphthol compared with tin dioxide nano particles
Mohammad Ali Zolfigol,*a Saeed Baghery,a Ahmad Reza Moosavi-Zare,*b Seyed Mohammad Vahdat,c
5
Heshmatollah Alinezhadd and Mohammad Norouzid,e
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
the particles with molecular ligands for the affecting of
cancerous cells, offers the outlook of more efficient cancer
1-Methylimidazolium tricyanomethanide {[HMIM]C(CN)3}
as a novel, green and nano molten salt catalyst was designed 10
and fully identified by IR, 1H NMR, 13C NMR, mass, thermal
gravimetric (TG), derivative thermal gravimetric (DTG), x-
ray diffraction patterns (XRD), scanning electron microscopy
(SEM) and transmission electron microscopy (TEM) analysis.
The catalytic application of {[HMIM]C(CN)3} was studied on 15
the preparation of 1-amidoalkyl-2-naphthols by the one-pot
three-component condensation reaction of various aromatic
aldehydes, amide and β-naphthol at room temperature under
solvent-free conditions in comparison with nano SnO2. In the
presented investigations, some products were produced and 20
reported for the first time.
treatment with reduced side-effects.9 A different strategy 50
for the use of nanoparticles in cancer therapy is photo-
thermal tumor ablation.10 Tin oxide (SnO2) is an
significant material because of its properties for example
low operating temperature, strong physical and chemical
interaction with adsorbed species, high degree of 55
transparency in the visible spectrum and strong thermal
stability in air (up to 500 oC).11 Tin dioxide, an n-type
semiconductor with a broad band gap (Eg = 3.6 eV, at 300
K), is a main functional material that has been widely
applied for optoelectronic devices.12 Tin oxide received 60
little consideration in the catalysis field compared to other
metal oxides.13 Although, tin oxide supported catalysts
have been described to be active for oxidative
dehydrogenation of propane, CO oxidation and
Introduction
Room-temperature molten salts (RTMSs), termed as
room-temperature ionic liquids, (RTILs), which are
immiscible or only partially miscible with water, have 25
been revealed to be promising as replacements to common
organic solvents. Molten salts (MSs) have important
potential as electrolyte materials. The molten salts, lately
called ionic liquids, have possessed very attention in
various scientific fields.1 Generally, MSs refer to inorganic 30
MSs and RTILs to organic onium salts molten below 100
oC. MSs are an attractive class of liquids due to their
incomparable ionic interactions and their varied number of
scientific usages.2, 3 Molten salts and ILs can be applied as
a GC stationary phases for both packed and open-tubular 35
columns.4-7
esterification reaction.14
65
Multicomponent reactions (MCRs) making heterocyclic
compounds are influential tools in the drug-discovery
process as they can offer appropriate synthesis of libraries
of druglike compounds in a single procedure.15 The one-
pot multi-component condensation reaction between 70
aromatic aldehydes with β-naphthol and amide derivatives
has been offered as a suitable synthetic method toward 1-
amidoalkyl-2-naphthols.16-23
1-Amidoalkyl-2-naphthols
are imperative intermediates which can be effortlessly
transformed into biologically active aminoalkyl naphthols 75
derivatives via amide hydrolysis. The hypertensive and
The nano sciences have lately developed as a main
study path of our modern society resulting from a
continuing attempt to miniaturize at the nano scale
operations that currently use microsystems. To this end, it 40
is well known that the bottom-up method should now
change the classic top-down one, a strategic move that is
common to various areas of nano sciences containing
sensing, medicine, opto-electronics and catalysis.8 More
lately, there have been developments towards biological 45
and medical usages of nanoparticles. The entrapment of
anticancer drugs in nanoparticles, and the decoration of
bradycardiac properties of these compounds have been
25
expected.24,
Several catalysts have been applied to
achieve this reaction, including boric acid,16 trityl
chloride,17 saccharin sulfonic acid (SASA),18 [Et3N– 80
SO3H]Cl,19 nano-S (S8-NP),20 [Msim]Cl, [Dsim]Cl,
[Msim]AlCl4,21 Fe(HSO4)322 and [2-MPyH]OTf.23
In this work, we have prepared a novel molten salt and
catalyst, namely 1-methylimidazolium tricyanomethanide
{[HMIM]C(CN)3} (Scheme 1) and used it for the 85
synthesis of 1-amidoalkyl-2-naphthol derivatives under
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solvent-free reaction conditions (Scheme 2). Also, to
compare the catalytic activity of [HMIM]C(CN)3 in nano
scale, SnO2 nanoparticles were applied instead of it in the
synthesis of 1-amidoalkyl-2-naphthol derivatives in
similar conditions.
Additionally, the 1H NMR and 13C NMR spectra of the
1-methylimidazolium tricyanomethanide in DMSO-d6 are
demonstrated in Figures 2 and 3, respectively. As Figures 55
1
2 and 3, indicate that, the main peak of H NMR spectra of
5
nano molten salt catalyst is related to N–H group on
methyl imidazolium ring of {[HMIM]C(CN)3} which is
observed in δ = 11.95 ppm. The peak related to methyl
group is appeared at 2.5 ppm and the peaks related to 60
imidazolium ring are depicted at 7.0 and 7.8 ppm
respectively. Also, the important peak of 13C NMR spectra
of nano molten salt catalyst is linked to the –CN group on
tricyanomethanide anion which is detected at δ = 74.8
ppm and corresponded peaks at 119.7 and 134.8 ppm are 65
related to carbons of imidazolium ring.
N
H2O (5 mL)
N
Me
N
N
H
N
N
10
N
Me
N
N
N
{[HMIM]C(CN)3}
Scheme 1. The synthesis of 1-methylimidazolium tricyanomethanide
{[HMIM]C(CN)3} as a nano molten salt catalyst
15
Nano cat a or b (1 mol%)
CHO
Solven-free, r.t.
O
OH
R'
NH2
NH
2
70
75
80
R
+
R
1
OH
R'
4
O
C(CN)3
3
N
H
N
{[HMIM]C(CN)3}:
Me
a: 1-Methylimidazolium tricyanomethanide as a nano molten salt
b: Tin dioxide nano particles (SnO2)
Scheme 2. The synthesis of 1-amidoalkyl-2-naphthol derivatives in the 20
presence of {[HMIM]C(CN)3} as nano molten salt (a) and SnO2 nano
particles (b) as green nano catalytic systems
Results and discussion
Fig. 2. The 1H NMR spectrum of the 1-methylimidazolium tricyanomethanide
Characterization of 1-methylimidazolium tricyanomethanide
{[HMIM]C(CN)3} as a nano molten salt catalyst
The structure of 1-methylimidazolium tricyanomethanide
as a novel nano malten salt catalyst was studied and
identified by FT-IR, 1H NMR, 13C NMR, mass, TG, DTG,
XRD, SEM and TEM analysis.
25
as a novel nano molten salt catalyst
85
The IR spectrum of the nano molten salt displayed a 30
special peak at 3417 cm−1 which can be related to N–H
stretching group on imidazolium ring. Furthermore, the
two peaks detected at 2170 cm−1 and 2081 cm−1 related to
vibrational modes of –CN bonds (Fig. 1).
90
35
95
40
Fig. 3. The 13C NMR spectrum of the 1-methylimidazolium tricyanomethanide
as a novel nano molten salt catalyst
100
Thermal gravimetric (TG) and derivative thermal
gravimetric (DTG) analysis of 1-methylimidazolium
tricyanomethanide was investigated at range of 25 to 600
°C, with a temperature increase rate of 10 °C.min-1 in a
nitrogen atmosphere. The results are depicted in Figures 4 105
and 5. The thermal gravimetric (TG) and derivative
thermal gravimetric (DTG) analysis of the nano molten
salt catalyst showed importance losses in one step, and
decomposed after 320 °C.
45
50
Fig. 1. The IR spectrum of 1-methylimidazolium tricyanomethanide (a);
tricyanomethane (b); 1-methylimidazole (c)
2
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60
65
70
5
10
Fig. 6. The x-ray diffraction (XRD) pattern of the 1-methylimidazolium
tricyanomethanide as a nano molten salt catalyst
Fig. 4. The thermal gravimetric (TG) analysis of nano molten salt catalyst
15
20
25
Table 1. X-ray diffraction (XRD) data for the 1-methylimidazolium
tricyanomethanide as a nano molten salt catalyst
Peak width [FWHM]
(degree)
Size
Inter planer
Entry
2θ
[nm]
distance [nm]
1
2
3
27.20
38.90
50.90
0.26
0.29
0.17
31.44
29.06
47.31
0.327462
0.231242
0.179181
75
Fig. 5. The derivative thermal gravimetric (DTG) analysis of nano molten salt
catalyst
80
Size, shape and morphology of 1-methylimidazolium
tricyanomethanide as the nano molten salt catalyst were 30
studied by x-ray diffraction (XRD) pattern, scanning
electron microscopy (SEM) and transmission electron
microscopy (TEM) imaging demonstrations. XRD patterns
of the catalyst {[HMIM]C(CN)3} was considered in a
domain of 10-90 degree (Figure 6). As it is shown at 35
Figure 6, XRD patterns showed diffraction lines of high
crystalline nature at 2θ ≈ 27.20o, 38.90o and 50.90o. Peak
width (FWHM), size and inter planer distance related to
XRD pattern of {[HMIM]C(CN)3} were investigated in
the 27.20o to 50.90o degree and the obtained results have 40
been summarized in Table 1. For example, assignments
for the highest diffraction line 27.20o offered that an
FWHM of 0.26 a crystallite size of the catalyst of ca.
31.44 nm via the Scherrer equation [D = Kλ/(βcosθ)]
(Where D is the crystallite size, K is the shape factor, 45
being corresponding to 0.9 , λ is the x-ray wavelength, β is
the full width at half maximum of the diffraction peak,
and θ is the Bragg diffraction angle in degree) and an inter
planer distance of 0.327462 nm (sing the similar highest
diffraction line at 27.20o) was calculated via the Bragg 50
equation: dhkl = λ/(2sinθ), (λ : Cu radiation (0.154178
nm) were achieved. Obtaining crystallite sizes from
various diffraction lines using the Scherrer equation were
found to be in the nanometer range (29.06-47.31 nm),
85
90
Fig. 7. Scanning electron microscopy (SEM) of the 1-methylimidazolium
tricyanomethanide as a nano molten salt catalyst
95
100
105
which is principally in
a good agreement with the 55
scanning electron microscopy (SEM) and transmission
electron microscopy (TEM) (Figures 7 and 8).
Fig.
8.
Transmission
electron
microscopy
(TEM)
of
the 110
1-methylimidazolium tricyanomethanide as a nano molten salt catalyst
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Characterization of tin dioxide (SnO2) as a nano particle
catalyst
The SnO2 nano particles (NPs) were synthesized and
investigated according to previous literature.13,14,26,27 Size,
shape and morphology of the SnO2 NPs catalyst were
investigated using XRD patterns, FE-SEM and TEM
imaging approaches. The x-ray diffraction (XRD) pattern
of SnO2 NPs is presented in Figure 9. The peaks at 2θ
values of 26.50°, 33.75°, 37.80°, 51.60°, and 54.85° can
55
5
60
be observed. The SnO2 product displays tetragonal 10
structure. With respect to the intensity ratio of major peak
detected at 2θ equal to 51.60°, the crystalline structure of
the catalyst can noticeably be recognized. The average
crystallite size was proposed using width line of the
diffraction peak in radians (β), Bragg angle in degrees (θ), 15
and Debye-Scherrer equation (Figure 9 and Table 2). The
average size of the catalyst, consequently, achieved from
this equation that was established to be in the nanometer
range (28.73-36.66 nm), which is basically in agreement
65
Fig. 11. Transmission electron microscopy (TEM) of the SnO2 NPs catalyst
Application of 1-methylimidazolium tricyanomethanide
nano MS and SnO2 NPs as a catalyst.
with the FE-SEM and TEM (Fig. 10 and Fig. 11).
20
25
30
35
At first, to optimize the reaction conditions, the
condensation reaction of naphthalene-1-carbaldehyde, 70
β-naphthol and acetamide was selected as a model and
different amounts of nano catalyst at range of 25–125 °C
were tested on it under solvent-free conditions (Table 3).
As shown in Table 3, the best results were attained when
the reaction was achieved in the presence of 1 mol% of 75
nano molten salt and SnO2 nanoparticles at room
temperature (Table 3, entry 5). No improvement was
observed in the yield of reaction by increasing the amount
of the nano catalysts and the temperature (Table 3, entries
6-13). Table 3 clearly demonstrates that in the absence of 80
nano catalyst, the product was not prepared. A slight
excess of the amide was established to be favorable and
hence the molar ratio of β-naphthol and aromatic aldehyde
to amide was considered at 1:1:1.2.
Fig. 9. The x-ray diffraction (XRD) pattern of the SnO2 NPs catalyst
Table 2. X-ray diffraction (XRD) data for the SnO2 NPs catalyst
Peak width [FWHM]
(degree)
Size
Inter planer
Entry
2θ
Table 3. Result of amount of the catalyst and temperature on the 85
condensation reaction of naphthalene-1-carbaldehyde, β-naphthol and
acetamide under solvent-free conditions
[nm]
distance [nm]
1
2
3
4
5
26.50
33.75
37.80
51.60
54.85
0.24
0.25
0.29
0.24
0.30
33.88
32.92
28.73
36.66
30.02
0.336245
0.265517
0.237654
0.177012
0.167028
Entry
Amount of
Reaction
Reaction time
(min)
Yield (%)
catalyst (mol%) temperature (oC)
Molten Nano Molten Nano
salt
SnO2
salt
SnO2
1
2
—
—
0.5
0.5
1
r.t.
100
r.t.
75
75
60
60
7
75
75
60
60
17
17
17
17
17
17
17
20
20
—
—
37
37
96
96
96
96
93
96
96
95
95
—
—
25
25
87
87
87
87
85
87
87
86
86
3
40
4
100
r.t.
5
6
1
50
7
7
1
75
7
8
1
100
125
r.t.
7
45
9
1
7
10
11
12
13
2
7
2
100
r.t.
7
5
10
10
5
100
Fig. 10. Field emission scanning electron microscopy (FE-SEM) of the SnO2 50
NPs catalyst
4
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28,29
To compare the effect of the solution in comparison with
solvent-free conditions, mixture of naphthalene-1-
product was obtained after aromatization.17-22,
50
a
Table 5. Synthesis of 1-amidoalkyl-2-naphthol derivatives using
1-methylimidazolium tricyanomethanide nano molten salt (1 mol%) and
SnO2 nano particles (1 mol%) as a catalyst
carbaldehyde, β-naphthol and acetamide as model
reaction, in the presence of 1 mol% of nano molten salt
and nano SnO2 as a catalyst in several solvents such as
H2O, C2H5OH, CH3CN, CH3CO2Et, CH2Cl2 and toluene
was considered at room temperature. The results are
depicted in Table 4. As it can be shown in Table 4,
solvent-free condition was the best condition in this
reaction.
5
Entry
Aldehyde
R'
Time (min)
Yield (%)
M.p (oC)
[Ref.]
Molten Nano Molten Nano
salt
25
SnO2
35
salt
90
SnO2
81
1
2
Benzaldehyde
NH2
177-179
[23]
10
Table 4. The effect of different solvents on the reaction of naphthalene-1-
carbaldehyde, β-naphthol and acetamide catalyzed by of nano molten salt
(1 mol%) and SnO2 NPs (1 mol%) at room temperature
4-Nitrobenzaldehyde NH2
4-Chlorobenzaldeyhe NH2
15
20
23
25
25
18
30
5
25
29
31
35
35
27
35
15
20
20
17
25
17
27
15
20
25
25
23
94
92
91
90
90
93
90
97
95
95
96
93
96
92
96
96
94
93
95
85
83
83
80
80
84
80
88
85
85
87
83
86
83
88
87
83
83
85
200-202
[23]
3
161-163
[23]
Entry
Solvent
Reaction time (min)
Yield (%)
Molten salt Nano SnO2 Molten salt Nano SnO2
4
2,5-
Dimethoxybenzaldehyde
Furfural
NH2
NH2
NH2
NH2
NH2
206-208
1
2
3
4
5
6
7
Solvent-free
H2O
7
30
30
30
60
75
120
17
30
96
25
25
20
10
—
—
87
15
25
20
10
—
—
5
140-142
[23]
C2H5OH
CH3CN
30
30
6
Thiophene-2-
carbaldehyde
Naphthalene-1-
carbaldehyde
α-
152-154
[23]
CH3CO2Et
CH2Cl2
60
75
7
195-197
[23]
Toluene
120
8
279-281
After optimization of the reaction conditions, to explore the
Methylcinnamaldehyde
efficiency and the scope of the presented protocol, several 15
1-amidoalkyl-2-naphthol derivatives were synthesized by
the three-component condensation reaction of various
aromatic aldehydes, β-naphthol and different amides in the
presence of a catalytic amount of 1-methylimidazolium
tricyanomethanide {[HMIM]C(CN)3} as a nano molten 20
salt catalyst and SnO2 as nano particles catalyst under
solvent-free reaction conditions. The results have been
represented in Table 5. The effect of substituents on the
aromatic ring were indicated estimated strong effects in
terms of yields under these reaction conditions. All 25
aromatic aldehydes including benzaldehyde and aldehydes
containing electron-releasing substituents, electron-
withdrawing substituents on their aromatic ring afforded
the related products in high to excellent yields in short
reaction times. The reaction times of aromatic aldehydes 30
having electron withdrawing groups were rather faster
than electron donating groups. Also, amide derivatives
similarly experienced well to the transformation.
Moreover, in this reaction condition acetamide was
reacted faster than benzamide and urea. Particularly, the 35
obtained results displayed that the nano molten salt (a) as
a catalyst was more successful than nanoparticles (b) in
this reaction conditions.
9
4-Nitrobenzaldehyde CH3
4-Chlorobenzaldeyhe CH3
248-250
[23]
10
11
12
13
14
15
16
17
18
19
20
10
12
7
258-260
[23]
2,5-
CH3
CH3
CH3
CH3
CH3
CH3
Ph
280-282
[23]
Dimethoxybenzaldehyde
Naphthalene-1-
carbaldehyde
265-267
Cinnamaldehyde
15
7
230-232
[16]
Naphthalene-2-
carbaldehyde
256-258
[20]
α-
20
8
223-225
Methylcinnamaldehyde
Biphenyl-4-
244-246
carbaldehyde
4-Nitribenzaldeyhe
8
253-255
[23]
4-Chlorobenzaldeyhe
Ph
15
18
10
205-207
[23]
2,5-
Dimethoxybenzaldehyde
Naphthalene-1-
carbaldehyde
Ph
271-273
Ph
293-295
In Scheme 3, we have suggested a possible mechanism for
the synthesis of 1-amidoalkyl-2-naphthol derivatives in 40
the presence of {[HMIM]C(CN)3} as a nano molten salt
catalyst and SnO2 nano particles as catalyst. The reaction
of aromatic aldehydes with β-naphthol in the presence of
nano catalyst is predictable to generate ortho-quinone
methides (o-QMs). The prepared o-QMs, have been 45
reacted with amide derivatives to give 1-amidoalkyl-2-
naphthol derivatives. A practical description for this result
can be given by considering the nucleophilic addition of
amide to o-QMs intermediate and lastly the desired
21
22
Cinnamaldehyde
Naphthalene-2-
carbaldehyde
Ph
Ph
18
10
30
23
92
95
82
85
201-203
264-266
23
24
α-
Ph
Ph
25
10
30
30
92
96
81
86
244-246
281-283
Methylcinnamaldehyde
Biphenyl-4-
carbaldehyde
55
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N
[HMIM]C(CN)3 as a nanostructured molten salt
NC
C(CN)3
N
H
N
N
O
NC
C
C
NC
N
H
Ar
H
NC
N
5
55
O
O
H
O
NH2
Ar
R
10
60
N
H
OH
NH
N
O
- H2O
C(CN)3
Ar
H
Fig. 12. Reusability of the nano MS catalyst in 7 minutes and nano NPs
R
O
catalyst in 17 minutes
o-QMs
SnO2 as nano particles
To compare the efficiency of our catalyst with some reported 65
catalysts for the synthesis of 1-amidoalkyl-2- naphthols, we
have tabulated the results of these catalysts to perform the
condensation of 4-chlorobenzaldehyde, β-naphthol and
acetamide, in Table 6. As Table 6 indicates, [HMIM]C(CN)3
has remarkably improved the synthesis of 1-amidoalkyl-2- 70
naphthols in different terms {reaction time, yield and turn-
over frequency (TOF)}. The TOF values were calculated by
the equation TOF = Yield (%)/[Time (min)×Catalyst amount
(mol%)]. The reaction times were shorter, and the yields and
OH
15
H
O
Ar
NH
Ar
H
Amphoteric effect
of SnO2
- H2O
R
O
O
O
NH2
Ar
R
Ar
H
H
SnO2
O
O
TOFs were higher when our catalysts were utilized.
75
o-QMs
Table 6. Comparison of the results on the condensation reaction of
4-chlorobenzaldehyde, β-naphthol and acetamide catalyzed by
[HMIM]C(CN)3 with those obtained by the recently reported
catalysts.
Scheme 3. Proposed mechanism for the synthesis of 1-amidoalkyl-2- naphthol 20
derivatives in the presence of {[HMIM]C(CN)3} as a nano MS and SnO2
as a NPs catalyst.
Furthermore, reusability of the catalyst was investigated upon
the condensation between naphthalene-1-carbaldehyde, β-
naphthol and acetamide. After the completion of the 25
reaction, ethyl acetate was added to the reaction mixture
and stirred and heated to separate product and remained
starting materials from the catalyst. This solution was
washed with water to separate catalyst from other
materials (the product and starting materials are soluble in 30
hot ethyl acetate and nano molten salt catalyst is soluble in
water). The aqueous layer was decanted and separated and
the catalyst was reused for alternative reaction after
removing of water. The catalytic activity of the catalyst
was restored within the limits of the experimental errors 35
for four continuous runs (Figure 12). For recycling of
SnO2 NPs, at the end of reaction, warm ethyl acetate was
added to the reaction mixture, stirred and heated to
separate product and remained starting materials from the
catalyst. Afterward, the obtained mixture, was centrifuged 40
to separate catalyst (SnO2 NPs catalyst is insoluble in
ethyl acetate and the reaction mixture is soluble in ethyl
acetate). The structure of reused [HMIM]C(CN)3 was also
Catalyst
loading
Time Yielda
TOFb
(min-
Reaction Condition
Ref.
(min)
(%)
Cu1.5PW12O40,
100 ◦C
2 mol%
5 mol%
90
78
0.433 [30 a]
0.125 [22]
Fe(HSO4)3,
85 ºC
Sulfamic acid,
ultrasound,
28-30 ◦C
45
88
92
51.5
mol%
120
0.015 [30 b]
I2, r.t.
5 mol%
690
10
90
90
0.026 [30 c]
0.900 [30 d]
Cyanuric chloride,
100 ◦C
10 mol%
H3PW12O40,
100 ◦C
2 mol%
80
88
85
0.550 [30 e]
0.070 [30 f]
4-(1-Imidazolium)
butane sulfonate,
80 ◦C
N-(4-sulfonic
acid)butyl
10 mol%
120
5
10
10
85
95
1.7
9.5
[30 g]
triethylammonium
hydrogensulfate,
c
-
[HMIM]C(CN)3, r.t.
1 mol%
a Isolated yield; b Turn-over frequency; c Our work
80
confirmed by IR, H NMR and 13C NMR spectra after its
1
The efficacy of SnO2 nano particles on the synthesis of 1-
amidoalkyl-2- naphthols was also studied in comparison with
some other dioxide catalysts such as CeO2, PbO2, TiO2, Ag-
TiO2 and ZrO2. For this purpose, the reaction of
4-chlorobenzaldehyde, β-naphthol and acetamide was 85
investigated in the persence of these catalysts (Table 7). As
shown in Table 7, synthesis of 1-amidoalkyl-2- naphthols in
application in the reaction. These presented spectra are in 45
a very good accordance with the spectra of fresh catalyst
(Figures S3, S4 and S5). Moreover, the size and
morphology of reused catalysts were studied by SEM and
TEM analysis. These studies were shown that the catalysts
were recovered in nano size (Figures S6 and S7).
50
6
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the presence of SnO2 NPs as a catalyst was the best
conditions (dioxide catalyst) in this reaction.
melting-point determination (Scheme 1).
1-Methylimidazolium tricyanomethanide
{[HMIM]C(CN)3}: M.p: >300 oC; Yield: 96% (0.498 g);
Table 7. Comparison synthesis of 1-amidoalkyl-2-naphthols using different
dioxide catalyst under solvent-free conditions at room temperaturea
Spectral data: IR (KBr): υ 3417, 2925, 2170, 2081, 1631,
1
1574, 1455 cm-1; H NMR (400 MHz, DMSO-d6): δ 3.63 55
Dioxide
Catalyst loading
Time (min)
Yieldb (%)
(s, 3H, —CH3), 7.00 (s, 2H, —CH); 7.63 (s, 1H, —CH),
11.95 (brs, 1H, —NH); 13C NMR (100 MHz, DMSO-d6): δ
46.4, 67.2, 74.8, 119.8, 134.9, 160.2; MS: m/z = 173 [M]+,
174 [M+H]+.
Nano-SnO2
CeO2
1 mol%
1 mol%
2 mol%
1 mol%
2 mol%
1 mol%
a
20
60
85
15
—
30
5
PbO2
120
30
Nano-TiO2
Nano-Ag-TiO2
ZrO2
60
General procedure for the preparation of tin dioxide nano 60
particles catalyst
30
45
Reaction condition: 4-chlorobenzaldehyde (1 mmol), β-naphthol (1 mmol),
acetamide (1.2 mmol); b Isolated yields.
5
SnO2 NPs were prepared using dissolving of 0.1 M: 2 g
stannous chloride dehydrate (SnCl2.2H2O) in 50 ml
distilled water. Afterward complete dissolution, ammonia
solution was added drop wise to the above solution and 65
stirred. The resulting gels were filtered and dried at 80 ºC
for 24 h in order to remove water. In conclusion, SnO2
NPs were formed at 600 ºC for 2h and which was
considered by x-ray diffraction patterns (XRD), field
emission scanning electron microscopy (FE-SEM) and 70
transmission electron microscopy (TEM) analysis.13,14,26,27
General procedure for the synthesis of 1-amidoalkyl-2-
naphthol derivatives
Conclusion
In summary, a novel, green and efficient nano molten salt
catalyst namely 1-Methyl imidazolium tricyanomethanide
{[HMIM]C(CN)3}
was
designed
and
completely 10
characterized by IR, 1H NMR, 13C NMR, mass, thermal
gravimetric (TG) and derivative thermal gravimetric (DTG),
x-ray diffraction patterns (XRD), scanning electron
microscopy (SEM) and transmission electron microscopy
(TEM) analysis. Catalytic application of {[HMIM]C(CN)3} 15
was studied on the synthesis of 1-amidoalkyl-2-naphthol
derivatives by the three-component condensation reaction of
various aromatic aldehydes, β-naphthol and several amide at
room temperature under solvent-free conditions. Moreover, to
compare the catalytic activity of the catalyst in similar 20
conditions nano SnO2 was used instead of {[HMIM]C(CN)3}
in the synthesis of 1-amidoalkyl-2-naphthol derivatives.
Generally, the achieved results showed that the
{[HMIM]C(CN)3} nano molten salt was more successful than
SnO2 nanoparticles as a catalyst (due to formation of products 25
with higher yields and shorter reaction time,
{[HMIM]C(CN)3} as a nano molten salt catalyst is better than
SnO2 nanoparticles as a catalyst). Additional studies indicated
that the nano molten salt basicity plays a main role in the
dual-catalyzed reactions. Various important advantages of 30
this study are relatively short reaction time, high yield,
cleaner reaction profile, low cost, simplicity of product
isolation, reusability of the nano catalyst and compliance with
the green chemistry protocols.
To a mixture of aromatic aldehydes (1mmol), β-naphthol
(1mmol) and amide derivatives (1.2 mmol) in a round 75
bottom flask connected to condenser,
1 mol% of
{[HMIM]C(CN)3} nano molten salt or SnO2 nano particles
was added as catalyst and the resulting mixture was firstly
stirred magnetically under solvent-free conditions at room
temperature for appropriate time. After completion of the 80
reaction as monitored by TLC (n-hexane/ethyl acetate:
5/1), ethyl acetate (10 mL) was added to reaction mixture,
stirred and refluxed for 5 min, and then washed with water
(10 mL) and decanted to separate catalyst from the other
materials (the reaction mixture was soluble in hot ethyl 85
acetate and nano molten salt catalyst was soluble in
water). The aqueous layer was decanted, separated and
after removing of water the remained catalyst was used for
alternative reaction. The solvent of organic layer was
removed and the crude product was purified by 90
recrystallization from ethanol (95%). Note: In another
procedure, for the recycle of SnO2 NPs, at the end of
reaction, warm ethyl acetate was added to the reaction
mixture and centrifuged to separate product and starting
materials from the catalyst (SnO2 NPs catalyst is insoluble 95
in ethyl acetate). In this work, nano molten salt and SnO2
nano particles as catalyst were recycled and reused for
four times without significant loss of its catalytic activity.
Spectral data analysis for compounds
Experimental
35
General procedure for the preparation of nano molten salt
catalyst: 1-methylimidazolium tricyanomethanide
1-Methylimidazole (3 mmol: 0.246 g) was added to 5 mL
an aqueous solution of tricyanomethane (3 mmol: 0.273 g)
and stirred at room temperature for 60 minutes. 40
Subsequently the solvent was removed by distillation
under reduced pressure; the white residue was dried under
1-((2-Hydroxynaphthalen-1-yl)(4-nitrophenyl)methyl)urea 100
o
(Table 3, entry 2): Yellow solid; M.p: 200-202 C; Yield:
o
vacuum at 100 C for 3 h. A pale pink solid formed which
(nano molten salt: 94%, nano SnO2: 85%); IR (KBr): υ
1
3484, 3457, 3316, 3074, 1655, 1604, 1516, 1348 cm-1; H
was filtered, washed with diethyl ether three times, and
then dried under vacuum (a pale pink solid was insoluble 45
NMR (400 MHz, DMSO-d6): δ 6.94 (brs, 1H, —OH), 7.48
(brs, 2H, —NH2), 7.61 (d, 1H, J = 9.2 Hz, —CH 105
aliphatic), 7.68 (d, 2H, J = 7.2 Hz, ArH), 7.94 (d, 2H, J =
8.8 Hz, ArH), 7.99 (t, 4H, J = 9.0 Hz, ArH), 8.04 (d, 2H, J
= 8.8 Hz, ArH), 8.71 (d, 1H, J = 8.4 Hz, —NH); 13C NMR
1
in diethyl ether) and which was characterized by IR, H
NMR, 13C NMR, mass, thermal gravimetric (TG) and
derivative thermal gravimetric (DTG), x-ray diffraction
patterns (XRD), scanning electron microscopy (SEM) and
transmission electron microscopy (TEM) analysis and 50
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DOI: 10.1039/C5RA02718G
(100 MHz, DMSO-d6): δ 36.7, 116.6, 118.2, 123.6, 124.2,
125.2, 127.7, 129.2, 129.5, 130.1, 131.1, 131.2, 146.3,
148.5, 153.1, 196.3.
47.5, 118.1, 123.8, 125.1, 127.5, 128.7, 128.8, 128.9,
129.0, 129.1, 129.2, 129.7, 130.1, 131.1, 131.2, 131.4, 60
144.9, 148.4, 191.5.
1-((2,5-Dimethoxyphenyl)(2-hydroxynaphthalen-1-
yl)methyl)urea (Table 3, entry 4): Pale yellow solid; M.p:
206-208 oC; Yield: (nano molten salt: 91%, nano SnO2:
83%); IR (KBr): υ 3493, 3386, 3082, 2994, 1662, 1529,
N-((2-hydroxynaphthalen-1-yl)(naphthalen-1-
5
yl)methyl)acetamide (Table 3, entry 12): White solid; M.p:
265-267 oC; Yield: (nano molten salt: 96%, nano SnO2:
87%); IR (KBr): υ 3413, 3057, 3006, 2937, 1647, 1628, 65
1
1
1495, 1271 cm-1; H NMR (400 MHz, DMSO-d6): δ 3.50
1582, 1512, 1332 cm-1; H NMR (400 MHz, DMSO-d6): δ
(s, 3H, —OCH3), 3.66 (s, 3H, —OCH3), 4.30 (brs, 2H, —
1.93 (s, 3H, —CH3), 7.25 (d, 2H, J = 8.8 Hz, ArH), 7.34
(t, 1H, J = 7.4 Hz, ArH), 7.43 (d, 1H, J = 8.0 Hz, —CH
aliphatic), 7.51 (t, 4H, J = 6.8 Hz, ArH), 7.64 (d, 1H, J =
8.0 Hz, ArH), 7.78 (d, 1H, J = 8.8 Hz, ArH), 7.83 (d, 1H, 70
J = 8.8 Hz, ArH), 7.94 (d, 1H, J = 9.6 Hz, ArH), 7.99 (d,
1H, J = 8.4 Hz, ArH), 8.06 (d, 1H, J = 9.2 Hz, ArH), 8.74
(d, 1H, J = 8.0 Hz, —NH), 10.05 (brs, 1H, —OH); 13C
NMR (100 MHz, DMSO-d6): δ 23.0, 47.4, 118.7, 119.1,
122.8, 123.6, 123.9, 125.6, 125.7, 125.9, 126.5, 126.7, 75
128.0, 129.0, 129.1, 129.2, 129.7, 131.5, 133.3, 134.0,
137.8, 153.8, 169.0; MS: m/z = 341 [M]+.
NH2), 6.75 (s, 1H, ArH), 6.81 (d, 1H, J = 9.2 Hz, —CH 10
aliphatic), 7.13 (d, 2H, J = 8.4 Hz, ArH), 7.19 (d, 1H, J =
8.4 Hz, ArH), 7.27 (t, 1H, J = 7.4 Hz, ArH), 7.44 (t, 1H, J
= 7.6 Hz, ArH), 7.69 (d, 1H, J = 8.8 Hz, ArH), 7.76 (d,
1H, J = 8.0 Hz, ArH), 8.18 (d, 1H, J = 8.8 Hz, ArH), 8.35
(d, 1H, J = 8.4 Hz, —NH), 9.83 (brs, 1H, —OH); 13C 15
NMR (100 MHz, DMSO-d6): δ 44.9, 55.7, 56.4, 111.5,
112.3, 116.3, 119.1, 119.3, 122.6, 123.8, 126.3, 128.6,
128.7, 129.2, 132.1, 133.0, 151.2, 153.2, 153.7, 168.8;
MS: m/z = 352 [M]+.
1-((2-Hydroxynaphthalen-1-yl)(naphthalen-1-
20
N-(1-(2-hydroxynaphthalen-1-yl)-3-phenylallyl)acetamide
o
(Table 3, entry 13): Yellow solid; M.p: 230-232 C; Yield:
yl)methyl)urea (Table 3, entry 7): Pale yellow solid; M.p:
195-197 oC; Yield: (nano molten salt: 93%, nano SnO2:
84%); IR (KBr): υ 3432, 3333, 3220, 2974, 1650, 1629,
(nano molten salt: 93%, nano SnO2: 83%); IR (KBr): υ 80
3417, 3175, 3065, 3023, 1657, 1642, 1515, 1439, 1270
cm-1; 1H NMR (400 MHz, DMSO-d6): δ 1.90 (s, 3H, —
CH3), 6.49 (d, 1H, J = 7.8 Hz, ArH), 6.60 (t, 1H, J = 7.4
Hz, —CH aliphatic), 6.67 (d, 1H, J = 5.6 Hz, ArH), 7.22
(t, 2H, J = 8.4 Hz, ArH), 7.31 (t, 3H, J = 7.2 Hz, ArH), 85
7.36 (d, 2H, J = 8.4 Hz, ArH), 7.47 (t, 1H, J = 7.2 Hz,
ArH), 7.75 (d, 1H, J = 8.8 Hz, ArH), 7.81 (d, 1H, J = 7.6
Hz, ArH), 8.14 (d, 1H, J = 8.4 Hz, ArH), 8.40 (d, 1H, J =
7.6 Hz, —NH), 10.04 (brs, 1H, —OH); 13C NMR (100
MHz, DMSO-d6): δ 23.1, 47.8, 118.8, 119.0, 122.9, 126.5, 90
126.7, 127.7, 128.9, 129.0, 129.1, 129.2, 129.5, 131.1,
132.5, 137.1, 153.5, 169.2.
1
1538, 1515 cm-1; H NMR (400 MHz, DMSO-d6): δ 5.40
(brs, 2H, —NH2), 5.70 (brs, 1H, —OH), 7.04 (d, 1H, J = 25
8.4 Hz, —CH aliphatic), 7.26 (d, 2H, J = 8.8 Hz, ArH),
7.35 (t, 1H, J = 7.4 Hz, ArH), 7.49 (t, 2H, J = 9.9 Hz,
ArH), 7.54 (d, 2H, J = 6.4 Hz, ArH), 7.77 (d, 2H, J = 8.8
Hz, ArH), 7.80 (d, 2H, J = 8.4 Hz, ArH), 7.95 (t, 2H, J =
7.0 Hz, ArH), 8.23 (d, 1H, J = 7.6 Hz, —NH); 13C NMR 30
(100 MHz, DMSO-d6): δ 47.8, 119.2, 119.8, 122.8, 123.0,
124.3, 125.2, 125.4, 125.5, 125.8, 126.0, 126.3, 126.8,
127.7, 128.9, 129.0, 129.1, 129.5, 131.4, 133.0, 134.0,
158.4.
1-(1-(2-Hydroxynaphthalen-1-yl)-2-methyl-3-
35
N-((2-hydroxynaphthalen-1-yl)(naphthalen-2-
phenylallyl)urea (Table 3, entry 8): Yellow solid; M.p:
279-281 oC; Yield: (nano molten salt: 90%, nano SnO2:
80%); IR (KBr): υ 3513, 3383, 3271, 3064, 2969, 1659,
yl)methyl)acetamide (Table 3, entry 14): White solid; M.p:
256-258 oC; Yield: (nano molten salt: 96%, nano SnO2: 95
86%); IR (KBr): υ 3407, 3153, 3060, 3011, 1644, 1629,
1
1
1600, 1230 cm-1; H NMR (400 MHz, DMSO-d6): δ 1.11
1514, 1271 cm-1; H NMR (400 MHz, DMSO-d6): δ 2.05
(s, 3H, —CH3), 4.53 (s, 1H, —CH), 5.41 (brs, 1H, —OH), 40
5.53 (d, 1H, J = 5.2 Hz, —CH aliphatic), 5.85 (brs, 2H, —
NH2), 6.96 (d, 1H, J = 5.0 Hz, ArH), 7.12 (t, 1H, J = 7.2
Hz, ArH), 7.20 (t, 2H, J = 7.4 Hz, ArH), 7.30 (d, 5H, J =
5.8 Hz, ArH), 7.42 (d, 1H, J = 6.4 Hz, —NH), 7.83 (t, 2H,
J = 9.0 Hz, ArH); 13C NMR (100 MHz, DMSO-d6): δ 13.5, 45
46.2, 75.9, 112.5, 119.0, 123.4, 123.5, 126.9, 128.7, 128.9,
129.0, 129.4, 129.6, 133.2, 146.2, 152.6, 157.8; MS: m/z =
332 [M]+.
(s, 3H, —CH3), 7.26 (d, 1H, J = 8.8 Hz, —CH aliphatic),
7.29 (d, 2H, J = 5.6 Hz, ArH), 7.34 (t, 2H, J = 5.6 Hz,
ArH), 7.47 (t, 2H, J = 5.6 Hz, ArH), 7.53 (d, 3H, J = 5.6 100
Hz, ArH), 7.83 (t, 3H, J = 7.6 Hz, ArH), 7.90 (s, 1H,
ArH), 8.59 (d, 1H, J = 8.4 Hz, —NH), 10.05 (brs, 1H, —
OH); 13C NMR (100 MHz, DMSO-d6): δ 23.2, 48.4, 119.0,
119.2, 122.9, 123.8, 124.2, 125.5, 125.9, 126.5, 126.8,
127.8, 128.0, 128.1, 129.0, 129.1, 129.9, 132.2, 132.9, 105
133.2, 140.8, 153.7, 169.9.
N-((4-chlorophenyl)(2-hydroxynaphthalen-1-
N-(1-(2-hydroxynaphthalen-1-yl)-2-methyl-3-
yl)methyl)acetamide (Table 3, entry 10): White solid; 50
M.p: 258-260 oC; Yield: (nano molten salt: 95%, nano
SnO2: 85%); IR (KBr): υ 3392, 3053, 2965, 1638, 1623,
phenylallyl)acetamide (Table 3, entry 15): White solid;
M.p: 223-225 oC; Yield: (nano molten salt: 92%, nano
SnO2: 83%); IR (KBr): υ 3395, 3055, 3023, 2965, 1627, 110
1524, 1515, 1371, 1274 cm-1; 1H NMR (400 MHz, DMSO-
d6): δ 1.67 (s, 3H, —CH3), 1.94 (s, 3H, —CH3), 6.45 (s,
1H, ArH), 6.53 (d, 1H, J = 8.4 Hz, —CH aliphatic), 7.22
(t, 4H, J = 8.8 Hz, ArH), 7.28 (d, 1H, J = 6.8 Hz, ArH),
7.34 (d, 2H, J = 7.6 Hz, ArH), 7.45 (t, 1H, J = 7.2 Hz, 115
ArH), 7.76 (d, 1H, J = 8.8 Hz, ArH), 7.81 (d, 1H, J = 7.6
1
1580, 1515, 1244 cm-1; H NMR (400 MHz, DMSO-d6): δ
2.30 (s, 3H, —CH3), 6.76 (d, 1H, J = 7.2 Hz, —CH
aliphatic), 7.22 (brs, 1H, —OH), 7.47 (d, 2H, J = 7.2 Hz, 55
ArH), 7.58 (d, 2H, J = 9.2 Hz, ArH), 7.66 (t, 4H, J = 8.4
Hz, ArH), 7.95 (d, 2H, J = 8.8 Hz, ArH), 8.68 (d, 1H, J =
8.4 Hz, —NH); 13C NMR (100 MHz, DMSO-d6): δ 36.2,
8
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Hz, ArH), 8.13 (d, 1H, J = 8.4 Hz, ArH), 8.28 (d, 1H, J =
8.4 Hz, —NH), 9.95 (brs, 1H, —OH); 13C NMR (100
MHz, DMSO-d6): δ 16.7, 23.1, 51.4, 117.8, 119.0, 122.8,
123.5, 123.6, 126.6, 126.7, 128.6, 128.9, 129.0, 129.1,
129.6, 133.4, 138.2, 138.5, 153.8, 169.5; MS: m/z = 331
[M]+.
SnO2: 85%); IR (KBr): υ 3424, 3128, 3031, 1629, 1536,
1
1342, 1250 cm-1; H NMR (400 MHz, DMSO-d6): δ 7.28 60
(d, 1H, J = 3.6 Hz, —CH aliphatic), 7.30 (d, 1H, J = 5.2
Hz, ArH), 7.40 (t, 3H, J = 6.0 Hz, ArH), 7.44 (d, 2H, J =
7.6 Hz, ArH), 7.51 (t, 1H, J = 7.2 Hz, ArH), 7.57 (d, 2H, J
= 8.0 Hz, ArH), 7.85 (t, 4H, J = 8.2 Hz, ArH), 7.90 (d, 1H,
J = 7.2 Hz, ArH), 7.95 (d, 1H, J = 8.0 Hz, ArH), 7.99 (d, 65
1H, J = 8.0 Hz, ArH), 8.09 (d, 1H, J = 7.6 Hz, ArH), 8.27
(d, 1H, J = 8.0 Hz, ArH), 9.26 (d, 1H, J = 8.4 Hz, —NH),
10.22 (brs, 1H, —OH); 13C NMR (100 MHz, DMSO-d6): δ
48.4, 118.3, 119.2, 122.9, 123.9, 125.7, 126.1, 126.5,
126.9, 127.9, 128.4, 128.7, 129.0, 129.1, 129.2, 129.8, 70
131.7, 131.8, 133.3, 134.1, 134.7, 136.7, 154.1, 165.8;
MS: m/z = 403 [M]+.
5
N-(biphenyl-4-yl(2-hydroxynaphthalen-1-
yl)methyl)acetamide (Table 3, entry 16): White solid; M.p:
244-246 oC; Yield: (nano molten salt: 96%, nano SnO2:
88%); IR (KBr): υ 3395, 3156, 3060, 3030, 3011, 1643, 10
1
1516, 1335 cm-1; H NMR (400 MHz, DMSO-d6): δ 2.00
(s, 3H, —CH3), 7.17 (d, 1H, J = 8.4 Hz, —CH aliphatic),
7.24 (t, 2H, J = 8.8 Hz, ArH), 7.27 (d, 1H, J = 8.8 Hz,
ArH), 7.34 (d, 2H, J = 7.6 Hz, ArH), 7.45 (t, 2H, J = 7.6
Hz, ArH), 7.56 (d, 2H, J = 7.6 Hz, ArH), 7.61 (d, 2H, J = 15
7.2 Hz, ArH), 7.79 (d, 1H, J = 8.8 Hz, ArH), 7.83 (d, 2H,
J = 7.6 Hz, ArH), 7.89 (t, 1H, J = 7.0 Hz, ArH), 8.51 (d,
1H, J = 8.4 Hz, —NH), 10.06 (brs, 1H, —OH); 13C NMR
(100 MHz, DMSO-d6): δ 23.1, 48.1, 118.9, 119.2, 122.9,
126.8, 127.0, 127.1, 127.7, 128.9, 129.0, 129.3, 129.8, 20
132.8, 138.5, 140.4, 142.4, 153.6, 169.8; MS: m/z = 367
[M]+.
N-(1-(2-hydroxynaphthalen-1-yl)-3-phenylallyl)benzamide
o
(Table 3, entry 21): Yellow solid; M.p: 201-203 C; Yield:
(nano molten salt: 92%, nano SnO2: 82%); IR (KBr): υ 75
1
3413, 3180, 3062, 3027, 1634, 1516, 1341, 1277 cm-1; H
NMR (400 MHz, DMSO-d6): δ 6.56 (d, 2H, J = 7.8 Hz,
ArH), 6.78 (t, 1H, J = 9.6 Hz, —CH aliphatic), 6.84 (t,
1H, J = 6.0 Hz, ArH), 7.21 (t, 2H, J = 6.2 Hz, ArH), 7.28
(t, 3H, J = 7.6 Hz, ArH), 7.39 (d, 2H, J = 7.2 Hz, ArH), 80
7.51 (t, 3H, J = 9.2 Hz, ArH), 7.76 (d, 1H, J = 8.8 Hz,
ArH), 7.83 (d, 1H, J = 8.4 Hz, ArH), 7.86 (d, 2H, J = 7.6
Hz, ArH), 8.30 (d, 1H, J = 8.4 Hz, ArH), 8.95 (d, 1H, J =
6.0 Hz, —NH), 10.22 (brs, 1H, —OH); 13C NMR (100
MHz, DMSO-d6): δ 49.2, 118.7, 119.1, 123.0, 123.3, 85
126.7, 126.9, 127.6, 127.6, 128.8, 129.0, 129.5, 129.8,
130.1, 131.7, 132.4, 134.9, 137.1, 153.6, 165.7, 182.9;
MS: m/z = 379 [M]+.
N-((2-hydroxynaphthalen-1-yl)(4-
nitrophenyl)methyl)benzamide (Table 3, entry 17): Yellow
solid; M.p: 253-255 oC; Yield: (nano molten salt: 96%, 25
nano SnO2: 87%); IR (KBr): υ 3435, 3415, 3181, 3082,
1
3069, 1637, 1600, 1577, 1516, 1345 cm-1; H NMR (400
MHz, DMSO-d6): δ 5.75 (brs, 1H, —OH), 7.29 (d, 1H, J =
8.8 Hz, —CH aliphatic), 7.34 (d, 1H, J = 7.6 Hz, ArH),
7.43 (d, 1H, J = 7.6 Hz, ArH), 7.50 (t, 1H, J = 7.4 Hz, 30
ArH), 7.61 (t, 2H, J = 7.6 Hz, ArH), 7.74 (dd, 2H, J = 8.0
Hz, ArH), 7.87 (dd, 2H, J = 8.8 Hz, ArH), 7.92 (d, 2H, J =
7.2 Hz, ArH), 8.10 (d, 2H, J = 8.0 Hz, ArH), 9.18 (d, 2H,
J = 8.0 Hz, ArH), 10.50 (brs, 1H, —NH); 13C NMR (100
MHz, DMSO-d6): δ 49.4, 121.4, 122.1, 123.0, 123.3, 35
127.5, 127.9, 128.0, 128.7, 128.8, 128.9, 129.2, 129.6,
130.0, 130.2, 130.5, 131.7, 132.1, 132.7, 133.8, 134.4,
135.0, 145.0, 193.7.
N-((2-hydroxynaphthalen-1-yl)(naphthalen-2-
yl)methyl)benzamide (Table 3, entry 22): Yellow solid; 90
M.p: 264-266 oC; Yield: (nano molten salt: 95%, nano
SnO2: 85%); IR (KBr): υ 3419, 3062, 3029, 1629, 1535,
1
1344, 1275 cm-1; H NMR (400 MHz, DMSO-d6): δ 7.29
(d, 1H, J = 9.2 Hz, —CH aliphatic), 7.33 (d, 1H, J = 7.6
Hz, ArH), 7.46 (d, 4H, J = 9.6 Hz, ArH), 7.48 (s, 1H, 95
ArH), 7.52 (d, 2H, J = 7.6 Hz, ArH), 7.58 (t, 1H, J = 7.2
Hz, ArH), 7.86 (t, 6H, J = 6.4 Hz, ArH), 7.93 (d, 2H, J =
7.2 Hz, ArH), 8.17 (d, 1H, J = 8.8 Hz, ArH), 9.15 (d, 1H,
J = 8.8 Hz, —NH), 10.38 (brs, 1H, —OH); 13C NMR (100
MHz, DMSO-d6): δ 49.9, 118.7, 119.2, 123.2, 123.3, 100
124.9, 125.8, 126.1, 126.6, 127.3, 127.7, 127.8, 127.9,
128.2, 128.3, 128.9, 129.0, 129.1, 130.0, 131.9, 132.4,
132.9, 133.2, 134.8, 140.1, 153.8, 166.5; MS: m/z = 403
[M]+.
N-((2,5-dimethoxyphenyl)(2-hydroxynaphthalen-1-
yl)methyl)benzamide (Table 3, entry 19): Yellow solid; 40
M.p: 271-273 oC; Yield: (nano molten salt: 93%, nano
SnO2: 83%); IR (KBr): υ 3420, 3160, 3065, 2993, 1640,
1577, 1526, 1492, 1275 cm-1; 1H NMR (400 MHz, DMSO-
d6): δ 3.61 (s, 3H, —CH3), 3.66 (s, 3H, —CH3), 6.80 (d,
1H, J = 3.2 Hz, ArH), 6.91 (d, 1H, J = 8.8 Hz, —CH 45
aliphatic), 7.09 (s, 1H, ArH), 7.20 (d, 1H, J = 8.8 Hz,
ArH), 7.30 (t, 1H, J = 7.4 Hz, ArH), 7.47 (t, 4H, J = 6.4
Hz, ArH), 7.52 (d, 1H, J = 7.2 Hz, ArH), 7.74 (d, 1H, J =
8.8 Hz, ArH), 7.80 (d, 1H, J = 8.4 Hz, ArH), 7.85 (d, 2H,
J = 7.2 Hz, ArH), 8.27 (d, 1H, J = 8.8 Hz, ArH), 8.84 (d, 50
1H, J = 8.0 Hz, —NH), 10.17 (brs, 1H, —OH); 13C NMR
(100 MHz, DMSO-d6): δ 45.8, 55.7, 56.6, 112.0, 112.5,
116.5, 119.0, 119.2, 123.0, 123.7, 126.6, 127.6, 128.7,
128.8, 128.9, 129.4, 131.4, 131.6, 133.0, 135.0, 151.4,
N-(1-(2-hydroxynaphthalen-1-yl)-2-methyl-3-
105
phenylallyl)benzamide (Table 3, entry 23): Yellow solid;
M.p: 244-246 oC; Yield: (nano molten salt: 92%, nano
SnO2: 81%); IR (KBr): υ 3419, 3065, 3026, 2905, 1629,
1
1514, 1340, 1272 cm-1; H NMR (400 MHz, DMSO-d6): δ
1.88 (s, 3H, —CH3), 6.41 (s, 1H, —CH), 6.75 (d, 1H, J = 110
8.4 Hz, —CH aliphatic), 7.20 (t, 3H, J = 7.0 Hz, ArH),
7.25 (d, 1H, J = 8.8 Hz, ArH), 7.32 (t, 3H, J = 5.8 Hz,
ArH), 7.47 (d, 2H, J = 7.2 Hz, ArH), 7.56 (d, 2H, J = 7.2
Hz, ArH), 7.82 (t, 2H, J = 9.6 Hz, ArH), 7.87 (d, 2H, J =
7.2 Hz, ArH), 8.23 (d, 1H, J = 8.4 Hz, ArH), 8.83 (d, 1H, 115
J = 8.4 Hz, —NH), 10.21 (brs, 1H, —OH); 13C NMR (100
153.3, 153.7, 165.5; MS: m/z = 413 [M]+.
55
N-((2-hydroxynaphthalen-1-yl)(naphthalen-1-
yl)methyl)benzamide (Table 3, entry 20): White solid;
M.p: 293-295 oC; Yield: (nano molten salt: 95%, nano
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 9

RSC Advances
Page 10 of 11
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DOI: 10.1039/C5RA02718G
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MHz, DMSO-d6): δ 16.7, 53.1, 117.5, 119.1, 123.0, 123.4,
124.9, 126.7, 127.0, 127.6, 128.6, 128.8, 128.9, 129.0,
129.2, 129.7, 131.8, 133.3, 135.0, 137.8, 137.9, 153.9,
166.2; MS: m/z = 393 [M]+.
J. L. Anderson, J. Ding, T. Welton and D. W. Armstrong, J. 60
Am. Chem. Soc. 2002, 124, 14247.
N-(biphenyl-4-yl(2-hydroxynaphthalen-1-
5
V. Ponec and G. C. Bond, ''Catalysis by Metals and
Alloys'', Elsevier, Amsterdam, 1995, 95; G. C. Bond,
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Oxford Science Publications, Clarendon Press, Oxford, 65
1987.
yl)methyl)benzamide (Table 3, entry 24): White solid;
M.p: 281-283 oC; Yield: (nano molten salt: 96%, nano
SnO2: 86%); IR (KBr): υ 3414, 3071, 3026, 2940, 1631,
1
1538, 1342 cm-1; H NMR (400 MHz, DMSO-d6): δ 7.28
(d, 1H, J = 8.8 Hz, —CH aliphatic), 7.33 (d, 2H, J = 7.2 10
Hz, ArH), 7.38 (t, 3H, J = 7.4 Hz, ArH), 7.45 (t, 2H, J =
7.6 Hz, ArH), 7.51 (t, 3H, J = 7.4 Hz, ArH), 7.61 (d, 5H, J
= 8.8 Hz, ArH), 7.83 (d, 1H, J = 8.8 Hz, ArH), 7.87 (d,
1H, J = 7.62 Hz, ArH), 7.90 (d, 2H, J = 8.4 Hz, ArH),
8.15 (d, 1H, J = 8.4 Hz, ArH), 9.10 (d, 1H, J = 8.8 Hz, — 15
NH), 10.41 (brs, 1H, —OH); 13C NMR (100 MHz,
DMSO-d6): δ 49.5, 118.7, 119.1, 123.2, 127.0, 127.1,
127.3, 127.5, 127.6, 127.8, 128.8, 129.0, 129.1, 129.4,
129.9, 131.9, 132.8, 134.7, 139.0, 140.4, 141.7,
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Notes and references
Faculty of Chemistry, Bu-Ali Sina University, Hamedan 6517838683,
a
Iran
b
Department of Chemistry, University of Sayyed Jamaleddin Asadabadi, 30
Asadabad 6541835583, Iran
c
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Department of Chemistry, Ayatollah Amoli Branch, Islamic Azad
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d Faculty of Chemistry, University of Mazandaran, Babolsar 47415, Iran
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e
Department of Chemistry, Payame Noor University, P.O. Box 19395- 35
3697, Tehran, Iran
*Corresponding Author: Fax: +988138257407
E-mail: zolfi@basu.ac.ir and mzolfigol@yahoo.com (M.A. Zolfigol);
moosavizare@yahoo.com (A.R. Moosavi-Zare).
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Abstract
20
Design of 1-methylimidazolium tricyanomethanide as the
first nanostructured molten salt and its catalytic
application on the condensation reaction of various
aromatic aldehydes, amide and β-naphthol compared with
tin dioxide nano particles
25
30
35
OH
NH
R
Nano cat a or b (1 mol%)
Solven-free, r.t.
R'
O
CHO
O
R'
NH2
R
+
C(CN)3
OH
N
H
N
Me
{[HMIM]C(CN)3}
a: 1-Methylimidazolium tricyanomethanide as a nano molten salt
b: Tin dioxide nano particles (SnO2)
Mohammad Ali Zolfigol,*a Saeed Baghery,a Ahmad Reza Moosavi-
Zare,*b Seyed Mohammad Vahdat,c Heshmatollah Alinezhadd and 40
Mohammad Norouzie
1-Methyl imidazolium tricyanomethanide {[HMIM]C(CN)3} as a novel nano
molten salt (MS) was synthesized and applied for the synthesis of
1-amidoalkyl-2-naphthols in comparison with tin dioxide (SnO2) nano
particles.
a
Faculty of Chemistry, Bu-Ali Sina University, Hamedan 6517838683,
45
Iran
b
Department of Chemistry, University of Sayyed Jamaleddin Asadabadi,
Asadabad 6541835583, Iran
c
Department of Chemistry, Ayatollah Amoli Branch, Islamic Azad 50
University, P.O. Box 678, Amol, Iran
d Faculty of Chemistry, University of Mazandaran, Babolsar 47415, Iran
e
Department of Chemistry, Payame Noor University, P.O. Box 19395-
3697, Tehran, Iran
*Corresponding Author: Fax: +988138257407
55
E-mail: zolfi@basu.ac.ir and mzolfigol@yahoo.com (M.A. Zolfigol);
moosavizare@yahoo.com (A.R. Moosavi-Zare).
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 11